Oil-soluble catalyst for coal / heavy oil hydro-conversion and application of oil-soluble catalyst

Abstract

The invention relates to a preparation method of an oil-soluble catalyst for coal / heavy oil hydro-conversion. The method comprises the following steps: mixing waste oil with formic acid, dropwise adding a hydrogen peroxide aqueous solution under stirring at 30-40 DEG C, carrying out a stirring reaction for 0.5-5 h after dropwise adding is completed, continuing stirring and heating to 40-80 DEG C, adding an alkali liquor, and carrying out a reaction for 0.5-3 h under stirring; dropwise adding an inorganic salt solution of active metal elements, and reacting for 0.1-0.5 hour while stirring; the obtained mixture is filtered and dried, the solid oil-soluble catalyst is obtained, and the active metal element is selected from one or more of Fe, Ni, Mo, Co or W. The invention further relates to an oil-soluble catalyst for coal / heavy oil hydro-conversion and application of the oil-soluble catalyst. The oil-soluble catalyst is high in catalytic activity, low in cost, high in dispersity, good in stability and easy to store, and the process operation cost is reduced.

Description

Technical Field

[0001] The invention belongs to the field of catalysts, and in particular relates to a preparation method of an oil-soluble catalyst for coal / heavy oil hydrogenation conversion, the oil-soluble catalyst and application thereof. Background Art

[0002] Clean and efficient utilization of coal and heavy oil resources to convert them into oil products and chemicals is an effective means to make up for the shortage of oil resources, accelerate economic development and reduce environmental pollution, and is also an important guarantee for energy security. Coal / heavy oil hydroconversion technology is a technology developed based on coal direct liquefaction technology to process coal and heavy oil together. Its basis is single coal direct liquefaction technology and heavy oil hydrocracking technology. Catalyst is the core technology of coal / heavy oil hydroconversion and coal direct liquefaction. It can effectively reduce the severity of the reaction, improve the utilization rate of activated hydrogen and the quality of liquid products, improve product quality, increase the conversion rate of coal, and improve the economy of the liquefaction process. It is currently a hot research topic in coal / heavy oil hydroconversion technology.

[0003] The development of coal / heavy oil hydroconversion catalysts has mainly gone through two stages: non-uniform solid powder catalysts and uniformly dispersed catalysts. Among them, uniformly dispersed catalysts include water-soluble dispersed catalysts and oil-soluble dispersed catalysts. Both catalysts exist in the form of metal particles and their sulfides in the reaction. The active metals are generally transition metals of IVB, VB, VIB, VIIB and VIIIB groups, and the most common ones are Fe, Ni, Co and Mo. Solid powder catalysts have obvious disadvantages. First, the tail oil contains a large number of solid particles, which are difficult to use and handle; second, they have low dispersion and short life. The dispersion process of water-soluble catalysts is complicated, the hydrogenation activity is low, and the coal conversion rate is low. Compared with water-soluble catalysts, oil-soluble catalysts have simple dispersion processes, high hydrogenation activity, and obvious coke inhibition. Therefore, the development of oil-soluble coal / heavy oil hydroconversion catalysts that are easier to prepare and store has become a topic of widespread concern.

[0004] CN111841630A discloses a fatty acid nickel oil-soluble catalyst for coal / heavy oil hydrogenation co-refining. The active ingredient of the catalyst is nickel, and the weight content of nickel in the catalyst is 6% to 20%. The preparation method comprises the following steps: (1) dissolving the fatty acid required for the reaction in ethanol, and fully mixing it with alkali solution, and adding a solvent, the reaction temperature is 60°C to 95°C, and the reaction time is 2 to 5 hours; (2) preparing a nickel salt aqueous solution, and adding it dropwise to the reaction system, controlling the drop rate to be 1 to 10 ml / min, the reaction temperature is 60°C to 95°C, and the reaction is continued for 2 to 5 hours after the dropwise addition is completed; (3) after the reaction is completed, the liquid is quickly separated, the aqueous phase is discarded, and the oil phase is washed with an appropriate amount of toluene or xylene, and then the solvent is evaporated and dried to obtain the fatty acid nickel oil-soluble catalyst. The catalyst prepared by the invention has good oil solubility, is fully in contact with the coal / heavy oil system and hydrogen during the reaction, has high catalytic hydrogenation activity and coke inhibition activity, and has a high coal conversion rate. However, the preparation process of the catalyst is harsh, and the raw materials fatty acid and nickel salt are relatively expensive, which further increases the cost of the catalyst. CN113492008A discloses a composite oil-soluble catalyst for coal tar slurry bed hydrogenation process. The patent discloses that oil is used as raw material to obtain a composite oil-soluble catalyst containing at least two metals. The preparation method comprises the following steps: (1) oil and alkali solution are charged into a reactor in proportion to perform saponification reaction, and boiled and refluxed for 0.5 to 2 hours under stirring; (2) metal inorganic salt and solvent are added, and displacement reaction is performed under stirring, and the reaction is performed at a temperature of 65°C to 95°C for 1 to 3 hours; (3) cooling and standing for stratification, separating the upper organic phase, and evaporating the solvent to obtain the composite oil-soluble catalyst; the catalyst prepared in the patent has good solubility and dispersion performance in coal tar, high catalytic activity, and high light oil yield, but the catalyst has poor stability and is not easy to store. Summary of the invention

[0005] The object of the present invention is to provide a method for preparing an oil-soluble catalyst for coal / heavy oil hydrogenation conversion, an oil-soluble catalyst and its application, and to use catering waste oil as a raw material to prepare an oil-soluble catalyst for coal / heavy oil hydrogenation conversion. The oil-soluble catalyst has high catalytic activity, low cost, high dispersibility, good stability, is easy to store, and reduces process operation costs.

[0006] To achieve one aspect of the above-mentioned invention object, the present invention provides a method for preparing an oil-soluble catalyst for coal / heavy oil hydrogenation conversion, the method comprising: mixing waste oil and formic acid, adding a hydrogen peroxide aqueous solution dropwise with stirring at 30°C-40°C, stirring and reacting for 0.5-5h after the addition is completed, continuing to stir and heat to 40-80°C, adding an alkali solution, and reacting for 0.5-3h under stirring; then adding an inorganic salt solution of an active metal element dropwise, and reacting for 0.1-0.5h under stirring; filtering and drying the obtained mixture to obtain a solid oil-soluble catalyst; the active metal element is selected from one or more of Fe, Ni, Mo, Co or W.

[0007] In a second aspect, the present invention provides an oil-soluble catalyst, which is prepared by the above method.

[0008] In a third aspect, the present invention provides an oil-soluble catalyst prepared by the above method or use of the above oil-soluble catalyst in coal / heavy oil hydrogenation conversion.

[0009] Compared with the prior art, the present invention has the following beneficial effects:

[0010] The method of the present invention is simple to operate, and the prepared oil-soluble catalyst has good solubility and dispersion performance in coal / heavy oil, high intrinsic activity, high stability, and is easy to store. The oil-soluble catalyst can further promote the conversion of coal / heavy oil during the coal / heavy oil hydrogenation reaction, and improve the coal conversion rate and oil yield. Moreover, the raw material source of the oil-soluble catalyst is wide and the cost is low; at the same time, the problem of the utilization of waste restaurant oil is solved, which not only reduces environmental pollution but also turns waste into treasure, and maximizes the use value of waste restaurant oil. DETAILED DESCRIPTION

[0011] Typical embodiments that embody the features and advantages of the present invention will be described in detail in the following description. It should be understood that the present invention can have various changes in different embodiments without departing from the scope of the present invention, and the descriptions therein are essentially used as illustrations rather than to limit the present invention.

[0012] In one aspect, the present invention provides a method for preparing an oil-soluble catalyst for coal / heavy oil hydrogenation conversion, the method comprising: mixing waste oil with formic acid, adding a hydrogen peroxide aqueous solution dropwise with stirring at 30°C-40°C, continuing to stir and react at 30°C-40°C for 0.5-5h after the addition is completed, continuing to stir and heat to 40°C-80°C, adding an alkali solution, and reacting for 0.5-3h under stirring; then adding an inorganic salt solution of an active metal element dropwise, and reacting for 0.1-0.5h under stirring; filtering and drying the obtained mixture to obtain a solid oil-soluble catalyst, wherein the active metal element is selected from one or more of Fe, Ni, Mo, Co or W.

[0013] In some embodiments, the waste oil and formic acid are mixed in a mass ratio of 6-15:5, preferably in a mass ratio of 6-10:5, such as 7:5, 8:5, or 9:5.

[0014] In some embodiments, the amount of the aqueous hydrogen peroxide solution is 0.5-1.5 times the mass of the waste oil, preferably 0.5-1 times, such as 0.6, 0.7, 0.8, or 0.9 times.

[0015] In some embodiments, the mass concentration of the aqueous hydrogen peroxide solution is 10%-50%, preferably 25%-35%, for example 30%.

[0016] In some embodiments, the alkali solution is one or more selected from sodium hydroxide aqueous solution or potassium hydroxide aqueous solution.

[0017] In some embodiments, the mass concentration of the alkali solution is 10%-50%, preferably 25%-35%, for example 30%.

[0018] In some embodiments, the mass ratio of the alkali solution to the waste oil is 1:1-5, preferably 1:2-4, for example 1:3.

[0019] In some embodiments, the inorganic salt of the active metal element may be a water-soluble metal inorganic salt, such as a water-soluble nitrate, sulfate, chloride, ammonium salt, etc.; the solvent is not particularly limited and may be water, such as deionized water. When the active metal element is two or more metal elements, the ratio of the two or more active metal elements in the inorganic salt of the active metal element is not particularly limited, and may be present in any ratio, for example.

[0020] In some embodiments, the mass ratio of the inorganic salt of the active metal element to the waste oil is 1:1-5.

[0021] In some embodiments, the waste oil comprises waste catering oil.

[0022] Furthermore, the waste cooking oil includes vegetable oil.

[0023] Furthermore, the vegetable oil comprises unsaturated fatty acids.

[0024] Furthermore, the vegetable oil comprises oleic acid and linoleic acid.

[0025] Preferably, the vegetable oil comprises one or more selected from peanut oil, soybean oil, walnut oil, sunflower seed oil, sesame oil, rice bran oil, corn oil, jatropha oil, palm oil, tung oil, coconut oil, cottonseed oil, camellia oil, rapeseed oil, safflower seed oil or peony seed oil.

[0026] In another aspect, the present invention also provides an oil-soluble catalyst, which is prepared by the above method.

[0027] In another aspect, the present invention also provides an oil-soluble catalyst prepared by the above method or the use of the above oil-soluble catalyst in coal / heavy oil hydrogenation conversion.

[0028] Usually, waste oil, especially restaurant waste oil, contains a large amount of unsaturated fatty acids mainly based on oleic acid, has unsaturated double bonds, and is mainly in liquid state. If the waste oil is directly treated with alkali solution and inorganic salts of active metal elements, the obtained catalyst is in a viscous liquid state, which is not easy to transport and store, and is easily oxidized and deteriorated in a short time, resulting in uncontrollable late catalytic process. The present invention uses formic acid as an oxygen carrier, reacts with hydrogen peroxide to generate peroxyformic acid, and the double bonds contained in the unsaturated fatty acids in the waste oil are first epoxidized, then hydrolyzed to obtain dihydroxyl groups, and then continues to react with alkali solution and inorganic salts of active metal elements in sequence to generate an oil-soluble catalyst in solid form, which has stable chemical properties, is easy to store and transport, and during the coal / heavy oil hydrogenation reaction, the oil-soluble catalyst can promote the conversion of coal / heavy oil, improve coal conversion rate and oil yield.

[0029] In the method of the present invention, if the amount of hydrogen peroxide is too little, the oxidation is not sufficient and the unsaturated double bonds in the waste oil cannot be epoxidized, but if the amount of hydrogen peroxide is too much, it will lead to deep oxidation, break the unsaturated bonds, generate a large number of by-products, shorten the carbon chain length, reduce lipophilicity, and reduce its oil solubility. At the same time, formic acid will participate in the reaction as an oxygen carrier in the oxidation reaction, but it will also make the reactants mutually soluble, so the amount of formic acid must be properly controlled. The method of the present invention obtains a catalyst for hydrogenation conversion with good oil solubility and high catalytic activity by properly controlling the amount of formic acid and hydrogen peroxide.

[0030] The embodiments of the present invention will be described in detail below in conjunction with specific examples, but it will be appreciated by those skilled in the art that the following examples are only used to illustrate the present invention and should not be considered to limit the scope of the present invention. In the examples, if specific conditions are not specified, the conditions are carried out according to normal conditions or manufacturer recommendations. If the reagents or instruments used do not specify the manufacturer, they are all conventional products that can be purchased commercially. In addition, the unspecified component ratios or contents in the present invention can all be any ratios or contents, and are not limited to the relationships such as mass ratio, concentration ratio, molar ratio or volume ratio.

[0031] Usually, the effective products of coal / heavy oil conversion into oil products mainly refer to n-hexane solubles, so in the examples, the test results are calculated based on the yield of n-hexane solubles. The calculation method complies with the national standard GB / T30044-2013.

[0032] Example 1

[0033] A method for preparing a Ni / Mo composite oil-soluble catalyst comprises the following steps: uniformly mixing 100g of kitchen waste peanut oil and 62.50g of formic acid, dripping 87.50g of a 30% hydrogen peroxide aqueous solution under stirring at 30°C, stirring and reacting for 3h at the same temperature, continuing heating and stirring to 60°C, adding 38.85g of a sodium hydroxide solution (9.96mol / L) for saponification reaction, reacting for 1.5h under stirring conditions, then dropwise adding 35.74g of nickel nitrate (3.37mol / L) and 34.70g of ammonium molybdate (3.82mol / L) for double decomposition reaction, reacting for 0.5h under stirring conditions, filtering the mixture, and drying it in a vacuum drying oven at 75°C for 24h to obtain a solid oil-soluble Ni / Mo composite catalyst, wherein the molar ratio of Ni to Mo is 1:1.

[0034] The Shangwan coal sample (dry ash-free basis), the prepared oil-soluble Ni / Mo composite catalyst, sulfur and tetralin were mixed and added into a 100mL high-pressure reactor. Among them, the mass ratio of the Shangwan coal sample to tetralin was 1:2; the molar ratio of sulfur to Ni+Mo was 2:1; the amount of the oil-soluble Ni / Mo composite catalyst (based on the mass of active metal Ni+Mo) added was 1wt% of the Shangwan coal sample. After replacing with 3MPa nitrogen for 3 times and then with 3MPa hydrogen for 3 times, hydrogen was filled to make the pressure reach 7MPa, and the temperature was raised from room temperature to 450℃ at a heating rate of 10℃ / min. After keeping the temperature constant for 1h, the temperature was rapidly cooled with a blower. The results showed that the yield of n-hexane soluble matter was 73wt.%.

[0035] Tahe residual oil, the prepared oil-soluble Ni / Mo composite catalyst, sulfur and tetralin were mixed and added into a 100mL high-pressure reactor. The mass ratio of Tahe residual oil to tetralin was 1:2; the molar ratio of sulfur to Ni+Mo was 2:1; the amount of oil-soluble Ni / Mo composite catalyst (based on the mass of active metal Ni+Mo) added was 1wt% of Tahe residual oil. After replacing with 3MPa nitrogen for 3 times and then with 3MPa hydrogen for 3 times, hydrogen was filled to make the pressure reach 7MPa, and the temperature was raised from room temperature to 450℃ at a heating rate of 10℃ / min. After being kept constant for 1h, the temperature was rapidly cooled with a blower. The results showed that the yield of n-hexane soluble matter was 89wt.%.

[0036] The Shangwan coal sample (dry ash-free basis), the prepared oil-soluble Ni / Mo composite catalyst, sulfur, Tahe residual oil and tetralin were mixed and added into a 100mL high-pressure reactor. Among them, the mass ratio of the Shangwan coal sample, tetralin and Tahe residual oil was 1:1:1; the molar ratio of sulfur to Ni+Mo was 2:1; the addition amount of the oil-soluble Ni / Mo composite catalyst (based on the mass of active metal Ni+Mo) was 1wt% of the total of the Shangwan coal sample and Tahe residual oil. After replacing with 3MPa nitrogen for 3 times and then with 3MPa hydrogen for 3 times, hydrogen was filled to make the pressure reach 7MPa, and the temperature was raised from room temperature to 450℃ at a heating rate of 10℃ / min. After being kept constant for 1h, the temperature was rapidly cooled with a blower. The results showed that the yield of n-hexane soluble matter was 68wt.%.

[0037] Example 2

[0038] A preparation method of a Fe / Ni / Mo composite oil-soluble catalyst comprises the following steps: 100 g of kitchen waste soybean oil and 62.50 g of formic acid are uniformly mixed, 87.50 g of a 30 wt% hydrogen peroxide aqueous solution is added dropwise under stirring at 35° C., the mixture is stirred for reaction at the same temperature for 2 h, the mixture is heated and stirred to 70° C., 38.85 g of a sodium hydroxide solution (9.96 mol / L) is added for saponification reaction, the mixture is stirred for reaction for 1.5 h, 18.00 g of ferric chloride (5.18 mol / L), 22.57 g of nickel nitrate (3.37 mol / L) and 24.20 g of ammonium molybdate (3.82 mol / L) are added dropwise for double decomposition reaction, the mixture is stirred for reaction for 0.5 h, the mixture is filtered and dried in a vacuum drying oven at 75° C. for 24 h to obtain a solid oil-soluble Fe / Ni / Mo composite catalyst, wherein the molar ratio of Fe, Ni and Mo is 1:1:1.

[0039] The Shangwan coal sample (dry ash-free basis), the prepared oil-soluble Fe / Ni / Mo composite catalyst, sulfur and tetralin were mixed and added into a 100mL high-pressure reactor. Among them, the mass ratio of the Shangwan coal sample to tetralin was 1:2; the molar ratio of sulfur to Fe+Ni+Mo was 2:1; the amount of the oil-soluble Fe / Ni / Mo composite catalyst (based on the mass of active metal Fe+Ni+Mo) added was 1wt% of the Shangwan coal sample. After replacing with 3MPa nitrogen for 3 times and then with 3MPa hydrogen for 3 times, hydrogen was filled to make the pressure reach 7MPa, and the temperature was raised from room temperature to 450℃ at a heating rate of 10℃ / min. After keeping the temperature constant for 1h, the temperature was rapidly cooled with a blower. The results showed that the yield of n-hexane soluble matter was 71wt.%.

[0040] Example 3

[0041] A preparation method of a Fe / Mo composite oil-soluble catalyst comprises the following steps: uniformly mixing 100 g of kitchen waste sunflower oil and 62.50 g of formic acid, dripping 87.50 g of a 30% hydrogen peroxide aqueous solution under stirring at 30° C., stirring and reacting at the temperature for 4 h, continuing heating and stirring to 80° C., adding 38.85 g of a sodium hydroxide solution (9.96 mol / L) for saponification reaction, reacting under stirring for 1.5 h, then dropwise adding 28.71 g of ferric chloride (5.18 mol / L) and 34.70 g of ammonium molybdate (3.82 mol / L) for double decomposition reaction, reacting under stirring for 0.5 h, filtering the mixture, and drying it in a vacuum drying oven at 75° C. for 24 h to obtain a solid oil-soluble Fe / Mo composite catalyst, wherein the molar ratio of Fe to Mo is 1:1.

[0042] The Shangwan coal sample (dry ash-free basis), the prepared oil-soluble Fe / Mo composite catalyst, sulfur and tetralin were mixed and added into a 100mL high-pressure reactor. Among them, the mass ratio of the Shangwan coal sample to tetralin was 1:2; the molar ratio of sulfur to Fe+Mo was 2:1; the amount of the oil-soluble Fe / Mo composite catalyst (based on the mass of active metal Fe+Mo) added was 1wt% of the Shangwan coal sample. After replacing with 3MPa nitrogen for 3 times and then with 3MPa hydrogen for 3 times, hydrogen was filled to make the pressure reach 7MPa, and the temperature was raised from room temperature to 450℃ at a heating rate of 10℃ / min. After keeping the temperature constant for 1h, the temperature was rapidly cooled with a blower. The results showed that the yield of n-hexane soluble matter was 70wt.%.

[0043] Example 4

[0044] A preparation method of a Fe / Ni composite oil-soluble catalyst comprises the following steps: uniformly mixing 100g of kitchen waste sesame oil and 62.50g of formic acid, adding 87.50g of a 30% aqueous hydrogen peroxide solution under stirring at 30°C, stirring and reacting for 5h at the same temperature, continuing heating and stirring to 80°C, adding 38.85g of a sodium hydroxide solution (9.96mol / L) for saponification reaction, reacting for 1.5h under stirring, then adding 28.71g of ferric chloride (5.18mol / L) and 35.74g of nickel nitrate (3.37mol / L) dropwise for double decomposition reaction, reacting for 0.5h under stirring, filtering the mixture, and drying it in a vacuum drying oven at 75°C for 24h to obtain a solid oil-soluble Fe / Ni composite catalyst, wherein the molar ratio of Fe to Ni is 1:1.

[0045] The oil-soluble Fe / Ni composite catalyst, sulfur and tetralin prepared from the Shangwan coal sample (dry ash-free basis) were mixed and added to a 100mL high-pressure reactor. Among them, the mass ratio of the Shangwan coal sample to tetralin was 1:2; the molar ratio of sulfur to Fe+Ni was 2:1; the amount of the oil-soluble Fe / Ni composite catalyst (based on the mass of active metal Fe+Ni) added was 1wt% of the Shangwan coal sample. After replacing with 3MPa nitrogen for 3 times and then with 3MPa hydrogen for 3 times, hydrogen was filled to make the pressure reach 7MPa, and the temperature was raised from room temperature to 450℃ at a heating rate of 10℃ / min. After being kept constant for 1h, the temperature was rapidly cooled with a blower. The results showed that the yield of n-hexane soluble matter was 68wt.%.

[0046] Example 5

[0047] A preparation method of a Fe / Co composite oil-soluble catalyst comprises the following steps: uniformly mixing 100 g of kitchen waste safflower seed oil and 62.50 g of formic acid, adding 87.50 g of a 30% hydrogen peroxide aqueous solution under stirring at 40° C., stirring and reacting for 5 hours at the same temperature, continuing heating and stirring to 80° C., adding 38.85 g of a sodium hydroxide solution (9.96 mol / L) for saponification reaction, reacting for 1.5 hours under stirring conditions, then adding 28.71 g of ferric chloride (5.18 mol / L) and 15.03 g of cobalt nitrate (3.63 mol / L) dropwise for double decomposition reaction, reacting for 0.5 hours under stirring conditions, filtering the mixture, and drying it in a vacuum drying oven at 75° C. for 24 hours to obtain a solid oil-soluble Fe / Co composite catalyst, wherein the molar ratio of Fe to Co is 1:1.

[0048] The Shangwan coal sample (dry ash-free basis), the prepared oil-soluble Fe / Co composite catalyst, sulfur and tetralin were mixed and added into a 100mL high-pressure reactor. Among them, the mass ratio of the Shangwan coal sample to tetralin was 1:2; the molar ratio of sulfur to Fe+Co was 2:1; the amount of the oil-soluble Fe / Co composite catalyst (based on the mass of active metal Fe+Co) added was 1wt% of the Shangwan coal sample. After replacing with 3MPa nitrogen for 3 times and then with 3MPa hydrogen for 3 times, hydrogen was filled to make the pressure reach 7MPa, and the temperature was raised from room temperature to 450℃ at a heating rate of 10℃ / min. After keeping the temperature constant for 1h, the temperature was rapidly cooled with a blower. The results showed that the yield of n-hexane soluble matter was 67wt.%.

[0049] Example 6

[0050] A method for preparing an Fe-based oil-soluble catalyst comprises the following steps: uniformly mixing 100 g of kitchen waste walnut oil and 62.50 g of formic acid, adding dropwise 87.50 g of a 30% aqueous hydrogen peroxide solution under stirring at 30° C., stirring and reacting at the same temperature for 5 h, continuing to heat and stir at 60° C., adding 38.85 g of a sodium hydroxide solution (9.96 mol / L) for saponification, reacting under stirring for 1.5 h, then adding dropwise 57.42 g of ferric chloride (5.18 mol / L) for double decomposition, reacting under stirring for 0.5 h, filtering the mixture, and drying it in a vacuum drying oven at 75° C. for 24 h to obtain a solid oil-soluble Fe-based catalyst.

[0051] The Shangwan coal sample (dry ash-free basis), the prepared oil-soluble Fe-based catalyst, sulfur and tetralin were mixed and added into a 100mL high-pressure reactor. Among them, the mass ratio of the Shangwan coal sample and tetralin was 1:2; the molar ratio of sulfur to Fe was 2:1; the amount of the oil-soluble Fe-based catalyst (based on the mass of active metal Fe) added was 1wt% of the Shangwan coal sample. After replacing with 3MPa nitrogen for 3 times and then with 3MPa hydrogen for 3 times, hydrogen was filled to make the pressure reach 7MPa, and the temperature was raised from room temperature to 450℃ at a heating rate of 10℃ / min. After keeping the temperature constant for 1h, the temperature was rapidly cooled with a blower. The results showed that the yield of n-hexane soluble matter was 64wt.%.

[0052] Example 7

[0053] This example was carried out in the same manner as Example 6, except that the amount of formic acid used was 83.3 g. As a result, the yield of n-hexane solubles was 63 wt.%.

[0054] Example 8

[0055] This example was carried out in the same manner as Example 6, except that the amount of formic acid used was 33.33 g. As a result, the yield of n-hexane solubles was 60 wt.%.

[0056] Example 9

[0057] This example was carried out in the same manner as Example 6, except that the amount of the aqueous hydrogen peroxide solution used was 50 g. As a result, the yield of the n-hexane soluble matter was 61 wt.%.

[0058] Example 10

[0059] This example was carried out in the same manner as Example 6, except that the amount of the aqueous hydrogen peroxide solution used was 150 g. As a result, the yield of the n-hexane soluble matter was 62 wt.%.

[0060] Comparative Example 1

[0061] The Shangwan coal sample (dry ash-free basis), Shenhua ultrafine hydrated iron oxide (FeOOH) catalyst, sulfur and tetralin were mixed and added into a 100mL high-pressure reactor. Among them, the mass ratio of the Shangwan coal sample to tetralin was 1:2; the molar ratio of sulfur to Fe was 2:1; the amount of FeOOH catalyst (based on the mass of active metal Fe) added was 1wt% of the Shangwan coal sample. After replacing with 3MPa nitrogen for 3 times and then with 3MPa hydrogen for 3 times, hydrogen was filled to make the pressure reach 7MPa, and the temperature was raised from room temperature to 450℃ at a heating rate of 10℃ / min. After keeping the temperature constant for 1h, the temperature was rapidly cooled with a blower. The results showed that the yield of n-hexane soluble matter was 58wt.%.

[0062] Comparative Example 2

[0063] The Shangwan coal sample (dry ash-free basis), analytical pure iron trioxide catalyst, sulfur and tetralin from Tianjin Beilian Fine Chemicals Development Co., Ltd. were mixed and added into a 100mL high-pressure reactor. Among them, the mass ratio of the Shangwan coal sample to tetralin is 1:2; the molar ratio of sulfur to Fe is 2:1; the amount of iron trioxide catalyst (based on the mass of active metal Fe) added is 1wt% of the Shangwan coal sample. After replacing with 3MPa nitrogen for 3 times and then with 3MPa hydrogen for 3 times, hydrogen was filled to make the pressure reach 7MPa, and the temperature was raised from room temperature to 450℃ at a heating rate of 10℃ / min. After keeping the temperature constant for 1h, the temperature was rapidly cooled with a blower. The results showed that the yield of n-hexane soluble matter was 57wt.%.

[0064] It can be seen that the catalytic effect of the catalyst of the present invention is greatly improved compared with the currently commercially available catalysts.

[0065] Comparative Example 3

[0066] The preparation method of the catalyst is the same as that of Example 6, except that the catalyst is not pretreated with formic acid and hydrogen peroxide. The catalyst is a viscous red liquid product with poor stability and high storage and transportation costs.

[0067] The Shangwan coal sample (dry ash-free basis), the obtained iron-based catalyst, sulfur and tetralin were mixed and added into a 100mL high-pressure reactor. Among them, the mass ratio of the Shangwan coal sample and tetralin was 1:2; the molar ratio of sulfur to Fe was 2:1; the amount of oil-soluble iron-based catalyst (based on the mass of active metal Fe) added was 1wt% of the Shangwan coal sample. After replacing with 3MPa nitrogen for 3 times and then with 3MPa hydrogen for 3 times, hydrogen was filled to make the pressure reach 7MPa, and the temperature was raised from room temperature to 450℃ at a heating rate of 10℃ / min. After keeping the temperature constant for 1h, the temperature was rapidly cooled with a blower. The results showed that the yield of n-hexane soluble matter was 59wt.%.

[0068] Unless otherwise defined, the terms used in the present invention have the meanings commonly understood by those skilled in the art.

[0069] The embodiments described in the present invention are for illustrative purposes only and are not intended to limit the scope of protection of the present invention. Those skilled in the art may make various other substitutions, changes and improvements within the scope of the present invention. Therefore, the present invention is not limited to the above embodiments.

Claims

1. A method for preparing an oil-soluble catalyst for coal / heavy oil hydroconversion, characterized in that: The method comprises: mixing waste oil with formic acid, adding a hydrogen peroxide aqueous solution under stirring at 30-40°C, stirring and reacting for 0.5-5h after the addition is completed, continuing to stir and heat to 40-80°C, adding alkali solution, and reacting for 0.5-3h under stirring; then adding an inorganic salt solution of an active metal element, and reacting for 0.1-0.5h under stirring; filtering and drying the obtained mixture to obtain a solid oil-soluble catalyst, wherein the active metal element is selected from one or more of Fe, Ni, Mo, Co or W.

2. The method for preparing an oil-soluble catalyst for coal / heavy oil hydroconversion according to claim 1, characterized in that: The waste oil and formic acid are mixed in a mass ratio of 6-15:5, preferably in a mass ratio of 6-10:5; And / or, the amount of the aqueous hydrogen peroxide solution is 0.5-1.5 times the mass of the waste oil, preferably 0.5-1 times.

3. The method for preparing an oil-soluble catalyst for coal / heavy oil hydroconversion according to claim 1, characterized in that: The mass concentration of the aqueous hydrogen peroxide solution is 10%-50%, preferably 25%-35%.

4. The method for preparing an oil-soluble catalyst for coal / heavy oil hydroconversion according to claim 1, characterized in that: The alkali solution includes one or more of a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution; And / or, the mass concentration of the alkali solution is 10%-50%, preferably 25%-35%.

5. The method for preparing an oil-soluble catalyst for coal / heavy oil hydroconversion according to claim 3, characterized in that: The mass ratio of the alkali solution to the waste oil is 1:1-5, preferably 1:2-4.

6. The method for preparing an oil-soluble catalyst for coal / heavy oil hydroconversion according to claim 1, characterized in that: The inorganic salt of the active metal element is a water-soluble metal inorganic salt.

7. The method for preparing an oil-soluble catalyst for coal / heavy oil hydroconversion according to claim 1, characterized in that: The mass ratio of the inorganic salt of the active metal element to the waste oil is 1:1-5.

8. The method for preparing an oil-soluble catalyst for coal / heavy oil hydroconversion according to any one of claims 1 to 7, characterized in that: The waste oil includes waste cooking oil; Preferably, the waste cooking oil comprises vegetable oil; Preferably, the vegetable oil comprises unsaturated fatty acids; Preferably, the vegetable oil comprises oleic acid and linoleic acid; Preferably, the vegetable oil comprises one or more selected from peanut oil, soybean oil, walnut oil, sunflower seed oil, sesame oil, rice bran oil, corn oil, jatropha oil, palm oil, tung oil, coconut oil, cottonseed oil, camellia oil, rapeseed oil, safflower seed oil or peony seed oil.

9. An oil-soluble catalyst, wherein the oil-soluble catalyst is prepared by the method according to any one of claims 1 to 8.

10. Use of the oil-soluble catalyst prepared by the method for preparing an oil-soluble catalyst for coal / heavy oil hydroconversion according to any one of claims 1 to 8 or the oil-soluble catalyst according to claim 9 in coal / heavy oil hydroconversion.