Oil-soluble catalyst for hydroconversion of coal and / or heavy oil and use thereof

Abstract

The present application relates to a kind of preparation methods of oil-soluble catalyst for coal and / or heavy oil hydroconversion, the method comprises: waste oil is mixed with formic acid, 30 ℃-40 ℃ under stirring dropwise adding aqueous hydrogen peroxide, after dropwise adding stirring reaction 0.5-5h, continue stirring and heat to 40 ℃-80 ℃, add lye, reaction 0.5-3h under stirring;Then dropwise adding inorganic salt solution of active metal element, reaction 0.1-0.5h under stirring;The mixture obtained is filtered, dried, to obtain the solid oil-soluble catalyst, the active metal element is one or more selected from Fe, Ni, Mo, Co or W.The present application also relates to an oil-soluble catalyst for coal and / or heavy oil hydroconversion and its application.The oil-soluble catalyst has high catalytic activity, low cost, high dispersibility, good stability, easy storage, and reduces process operating cost.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of catalysts, and particularly relates to a preparation method of an oil-soluble catalyst for coal and / or heavy oil hydroconversion, the oil-soluble catalyst and application thereof. BACKGROUND

[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 an important guarantee for energy security. Coal / heavy oil hydroconversion technology is a technology for processing coal and heavy oil together based on coal direct liquefaction technology, and its foundation is single coal direct liquefaction technology and heavy oil hydrocracking technology. Catalysts are the core technology of coal / heavy oil hydroconversion and coal direct liquefaction, which can effectively reduce the reaction severity, improve the utilization rate of activated hydrogen and the quality of liquid products, improve the product quality, increase the conversion rate of coal and the economic efficiency of the liquefaction process, and are the research focus of current coal / heavy oil hydroconversion technology.

[0003] The development of coal / heavy oil hydroconversion catalysts mainly experienced two stages of non-uniform solid powder catalysts and uniformly dispersed catalysts, and the uniformly dispersed catalysts include water-soluble dispersed catalysts and oil-soluble dispersed catalysts. Both of the two catalysts exist in the form of metal particles and sulfides in the reaction. The active metals are generally transition metals of groups IVB, VB, VIB, VIIB and VIIIB, and the most common ones are Fe, Ni, Co and Mo. The solid powder catalyst has obvious shortcomings, one is that a large amount of solid particles are contained in the tail oil, which is difficult to utilize and handle; the other is that it has low dispersion and short service life. The dispersion process of water-soluble catalysts is complex, and the hydrogenation activity is low, and the coal conversion rate is low. Compared with water-soluble catalysts, oil-soluble catalysts have simple dispersion process, high hydrogenation activity and obvious coke inhibition. Therefore, the development of oil-soluble coal / heavy oil hydroconversion catalysts which are easier to prepare and store has become a widely concerned topic.

[0004] CN111841630A discloses a kind of fatty acid nickel oil-soluble catalyst for coal / heavy oil hydrocracking, and the active ingredient of the catalyst is nickel, and the weight content of nickel in the catalyst is 6%~20%, and its preparation method includes the following steps: (1) the fatty acid required for reaction is dissolved in ethanol, and is mixed with lye, and solvent is added, and the reaction temperature is 60~95 DEG C, and the reaction time is 2~5h;(2) prepare nickel salt aqueous solution, and drop into the reaction system drop by drop, control the drop rate to be 1~10ml / min, the reaction temperature is 60~95 DEG C, after drop completion, continue to react 2~5h;(3) reaction is finished, quickly separates, discards water phase, oil phase is washed with appropriate amount of toluene or xylene after spin-evaporating solvent and drying, and fatty acid nickel oil-soluble catalyst is obtained;The catalyst prepared by the application has good oil solubility, and is fully contacted with coal / heavy oil system and hydrogen during reaction, has high catalytic hydrogenation activity and anticoking activity, and high coal conversion rate.But the preparation process of the catalyst is harsh, and raw material fatty acid and nickel salt are relatively expensive, which further increases the cost of catalyst.CN113492008A discloses a kind of compound oil-soluble catalyst for coal tar slurry bed hydrogenation process, and the patent discloses that oil is used as raw material to obtain a compound oil-soluble catalyst containing at least two kinds of metals, and its preparation method includes the following steps: (1) oil, lye are loaded into reaction kettle according to proportion and carry out saponification reaction, and boil reflux reaction under the condition of stirring for 0.5~2h;(2) add metal inorganic salt and solvent, and carry out displacement reaction under the condition of stirring, and react at 65~95 DEG C for 1~3h;(3) cooling and standing stratification, separate upper organic phase, evaporate solvent to obtain compound oil-soluble catalyst;The catalyst prepared by 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

[0005] The application aims to provide a preparation method of oil-soluble catalyst for coal and / or heavy oil hydroconversion, an oil-soluble catalyst and its application, which uses catering waste oil as raw material to prepare oil-soluble catalyst for coal and / or heavy oil hydroconversion, and the oil-soluble catalyst has high catalytic activity, low cost, high dispersibility, good stability, is easy to store, and reduces process operation cost.

[0006] To achieve the above-mentioned object, the present application provides a preparation method of an oil-soluble catalyst for coal and / or heavy oil hydroconversion, which comprises: mixing waste oil and formic acid, stirring and adding hydrogen peroxide aqueous solution at 30-40 DEG C, continuing stirring and reacting for 0.5-5 h after the addition is completed, continuing stirring and heating to 40-80 DEG C, adding alkali liquor, and reacting for 0.5-3 h under stirring; then adding an inorganic salt solution of active metal elements under stirring and reacting for 0.1-0.5 h; filtering and drying the obtained mixture to obtain the solid oil-soluble catalyst; and the active metal elements are selected from one or more of Fe, Ni, Mo, Co or W.

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

[0008] In a third aspect, the present application provides the oil-soluble catalyst prepared by the above-mentioned method or the application of the above-mentioned oil-soluble catalyst in coal and / or heavy oil hydroconversion.

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

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

[0011] The typical embodiments embodying the features and advantages of the present application will be described in detail hereinafter with reference to the accompanying drawings. It should be understood that the present application can have various changes in different embodiments, which do not deviate from the scope of the present application, and the description herein is essentially used for illustration, not for limiting the present application.

[0012] In one aspect, the present application provides a preparation method of an oil-soluble catalyst for coal and / or heavy oil hydroconversion, which comprises: mixing waste oil and formic acid, stirring and adding hydrogen peroxide aqueous solution at 30-40 DEG C, continuing stirring and reacting for 0.5-5 h after the addition is completed, continuing stirring and heating to 40-80 DEG C, adding alkali liquor, and reacting for 0.5-3 h under stirring; then adding an inorganic salt solution of active metal elements under stirring and reacting for 0.1-0.5 h; filtering and drying the obtained mixture to obtain the solid oil-soluble catalyst, and the active metal elements are selected from one or more of Fe, Ni, Mo, Co or W.

[0013] In some embodiments, the waste oil is mixed with formic acid at a mass ratio of 6-15:5, preferably at a mass ratio of 6-10:5, for example 7:5, 8:5, 9:5.

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

[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 aqueous sodium hydroxide or aqueous potassium hydroxide.

[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 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 can be a water-soluble metal inorganic salt, for example a water-soluble nitrate, sulfate, chloride, ammonium salt, etc.; the solvent is not particularly limited and can be water, for example 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 can be present in any ratio.

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

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

[0022] Further, the catering waste oil comprises vegetable oil.

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

[0024] Further, 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, oil tea camellia seed oil, rapeseed oil, safflower seed oil or peony seed oil.

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

[0027] In another aspect, the present application also provides an application of the oil-soluble catalyst prepared by the above method or the above oil-soluble catalyst in the hydroconversion of coal and / or heavy oil.

[0028] Generally, waste oil, especially catering waste oil, contains a large amount of unsaturated fatty acids mainly in the form of oleic acid, and the unsaturated double bonds exist mainly in liquid state. If the waste oil is directly treated by alkali and inorganic salt of active metal element, the obtained catalyst is in viscous liquid state, which is not easy to transport and store, and is prone to oxidation and deterioration in a short time, resulting in uncontrollable catalytic process in the later stage. In the present application, formic acid is used as an oxygen carrier to react with hydrogen peroxide to generate peroxymonocarbonate, and the double bonds contained in the unsaturated fatty acids in the waste oil are first epoxidized, then hydrolyzed to obtain dihydroxy, and then successively reacted with alkali and inorganic salt of active metal element to generate an oil-soluble catalyst in solid form. The oil-soluble catalyst has stable chemical properties, is easy to store and transport, and can promote the conversion of coal and / or heavy oil, improve the coal conversion rate and oil yield during the hydrogenation reaction of coal and / or heavy oil.

[0029] In the method of the present application, if the amount of hydrogen peroxide is too small, the oxidation is not sufficient enough to epoxidize the unsaturated double bonds in the waste oil, but if the amount of hydrogen peroxide is too large, it will lead to deep oxidation, break the unsaturated bonds, generate a large amount of by-products, shorten the carbon chain length, and reduce the lipophilicity, thereby reducing the 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 application controls the amounts of formic acid and hydrogen peroxide to obtain a hydrogenation conversion catalyst with good oil solubility and high catalytic activity.

[0030] The embodiments of the present application will be described in detail below with reference to specific examples, but those skilled in the art will understand that the following examples are only used to illustrate the present application and should not be regarded as limiting the scope of the present application. If the specific conditions are not specified in the examples, the conventional conditions or the conditions recommended by the manufacturer are used. If the reagents or instruments used are not specified by the manufacturer, they are all conventional products that can be purchased on the market. In addition, the proportions or contents of the components not specified in the present application can be any proportion or content, and are not limited to the relationship of mass ratio, concentration ratio, molar ratio or volume ratio, etc.

[0031] Generally, the effective product of coal and / or heavy oil conversion into oil products mainly refers to n-hexane solubles, and therefore in the examples, the test results are calculated based on the yield of n-hexane solubles. The calculation method follows the national standard GB / T 30044-2013.

[0032] Example 1

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

[0034] After the Shangwan coal sample (dry ash-free basis), the prepared oil-soluble Ni / Mo composite catalyst, sulfur, and tetrahydronaphthalene are mixed and added to a 100 mL high-pressure reaction kettle. The mass ratio of the Shangwan coal sample to tetrahydronaphthalene is 1:2; the molar ratio of sulfur to Ni+Mo is 2:1; and the addition amount of the oil-soluble Ni / Mo composite catalyst (based on the mass of active metals Ni+Mo) is 1 wt% of the Shangwan coal sample. After being replaced with 3 MPa nitrogen for 3 times and then replaced with 3 MPa hydrogen for 3 times, hydrogen is filled to make the pressure reach 7 MPa, the temperature is raised from room temperature to 450°C at a temperature rising rate of 10°C / min, and then the temperature is kept constant for 1 h before rapid cooling with a blower. The results show that the n-hexane soluble yield is 73 wt.%.

[0035] After the Tahe residue oil, the prepared oil-soluble Ni / Mo composite catalyst, sulfur, and tetrahydronaphthalene are mixed and added to a 100 mL high-pressure reaction kettle. The mass ratio of the Tahe residue oil to tetrahydronaphthalene is 1:2; the molar ratio of sulfur to Ni+Mo is 2:1; and the addition amount of the oil-soluble Ni / Mo composite catalyst (based on the mass of active metals Ni+Mo) is 1 wt% of the Tahe residue oil. After being replaced with 3 MPa nitrogen for 3 times and then replaced with 3 MPa hydrogen for 3 times, hydrogen is filled to make the pressure reach 7 MPa, the temperature is raised from room temperature to 450°C at a temperature rising rate of 10°C / min, and then the temperature is kept constant for 1 h before rapid cooling with a blower. The results show that the n-hexane soluble yield is 89 wt.%.

[0036] The Shangwan coal sample (dry ash-free basis), the prepared oil-soluble Ni / Mo composite catalyst, sulfur, Tahe residue and tetrahydronaphthalene were mixed and then added into a 100 mL high-pressure reaction kettle. The mass ratio of the Shangwan coal sample, tetrahydronaphthalene and Tahe residue was 1:1:1; the molar ratio of sulfur to Ni+Mo was 2:1; and the addition amount of the oil-soluble Ni / Mo composite catalyst (based on the mass of active metals Ni+Mo) was 1 wt% of the total amount of the Shangwan coal sample and Tahe residue. After being replaced with 3 MPa nitrogen for 3 times and then replaced with 3 MPa hydrogen for 3 times, hydrogen was filled to make the pressure reach 7 MPa. After the temperature was raised from room temperature to 450°C at a temperature raising rate of 10°C / min, the temperature was kept constant for 1 h, and then the temperature was rapidly lowered by using a blower. The results showed that the n-hexane soluble yield was 68 wt.%.

[0037] Example 2

[0038] A preparation method of a Fe / Ni / Mo composite oil-soluble catalyst: 100 g of kitchen waste soybean oil and 62.50 g of formic acid were uniformly mixed, and then 87.50 g of a hydrogen peroxide aqueous solution with a mass concentration of 30 wt% was added dropwise under stirring at 35°C. After stirring and reaction at the temperature for 2 h, the mixture was continuously heated and stirred to 70°C, and 38.85 g of a sodium hydroxide solution (9.96 mol / L) was added for saponification reaction. After stirring for 1.5 h, 18.00 g of iron 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) were added dropwise for double decomposition reaction. After stirring for 0.5 h, the mixture was filtered and dried in a vacuum drying box 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 was 1:1:1.

[0039] The Shangwan coal sample (dry ash-free basis), the prepared oil-soluble Fe / Ni / Mo composite catalyst, sulfur and tetrahydronaphthalene were mixed and then added into a 100 mL high-pressure reaction kettle. The mass ratio of the Shangwan coal sample and tetrahydronaphthalene was 1:2; the molar ratio of sulfur to Fe+Ni+Mo was 2:1; and the addition amount of the oil-soluble Fe / Ni / Mo composite catalyst (based on the mass of active metals Fe+Ni+Mo) was 1 wt% of the Shangwan coal sample. After being replaced with 3 MPa nitrogen for 3 times and then replaced with 3 MPa hydrogen for 3 times, hydrogen was filled to make the pressure reach 7 MPa. After the temperature was raised from room temperature to 450°C at a temperature raising rate of 10°C / min, the temperature was kept constant for 1 h, and then the temperature was rapidly lowered by using a blower. The results showed that the n-hexane soluble yield was 71 wt.%.

[0040] Example 3

[0041] A preparation method of an Fe / Mo composite oil-soluble catalyst: 100 g of kitchen waste sunflower seed oil and 62.50 g of formic acid are uniformly mixed, and then 87.50 g of a 30% hydrogen peroxide aqueous solution is added dropwise under stirring at 30°C; then, after stirring and reaction at the temperature for 4 h, the mixture is continuously heated and stirred to 80°C, 38.85 g of a sodium hydroxide solution (9.96 mol / L) is added for saponification reaction, and then the mixture is stirred and reacted for 1.5 h; then, 28.71 g of iron chloride (5.18 mol / L) and 34.70 g of ammonium molybdate (3.82 mol / L) are added dropwise for double decomposition reaction, and then the mixture is stirred and reacted for 0.5 h; then, the mixture is filtered, and dried in a vacuum drying box at 75°C for 24 h to obtain a solid Fe / Mo composite oil-soluble catalyst, wherein the molar ratio of Fe to Mo is 1:1.

[0042] The obtained Fe / Mo composite oil-soluble catalyst, sulfur, and tetrahydronaphthalene are mixed and then added into a 100 mL high-pressure reaction kettle. The mass ratio of the Shangwan coal sample to tetrahydronaphthalene is 1:2; the molar ratio of sulfur to Fe+Mo is 2:1; and the addition amount of the Fe / Mo composite oil-soluble catalyst (based on the mass of active metals Fe+Mo) is 1 wt% of the Shangwan coal sample. The mixture is replaced with 3 MPa nitrogen for 3 times, and then replaced with 3 MPa hydrogen for 3 times; then, hydrogen is filled to make the pressure reach 7 MPa; then, the temperature is increased from room temperature to 450°C at a temperature increasing rate of 10°C / min; then, the temperature is kept constant for 1 h; and then, the temperature is rapidly decreased by using a blower. The results show that the n-hexane soluble yield is 70 wt.%.

[0043] Example 4

[0044] A preparation method of an Fe / Ni composite oil-soluble catalyst: 100 g of kitchen waste sunflower seed oil and 62.50 g of formic acid are uniformly mixed, and then 87.50 g of a 30% hydrogen peroxide aqueous solution is added dropwise under stirring at 30°C; then, after stirring and reaction at the temperature for 4 h, the mixture is continuously heated and stirred to 80°C, 38.85 g of a sodium hydroxide solution (9.96 mol / L) is added for saponification reaction, and then the mixture is stirred and reacted for 1.5 h; then, 28.71 g of iron chloride (5.18 mol / L) and 34.70 g of ammonium molybdate (3.82 mol / L) are added dropwise for double decomposition reaction, and then the mixture is stirred and reacted for 0.5 h; then, the mixture is filtered, and dried in a vacuum drying box at 75°C for 24 h to obtain a solid Fe / Mo composite oil-soluble catalyst, wherein the molar ratio of Fe to Mo is 1:1.

[0045] The oil-soluble Fe / Ni composite catalyst prepared from the Shangwan coal sample (dry ash-free basis), sulfur, and tetrahydronaphthalene was mixed and added to a 100 mL high-pressure reaction kettle. The mass ratio of the Shangwan coal sample to tetrahydronaphthalene was 1:2; the molar ratio of sulfur to Fe+Ni was 2:1; and the addition amount of the oil-soluble Fe / Ni composite catalyst (based on the mass of active metals Fe+Ni) was 1 wt% of the Shangwan coal sample. After being replaced with 3 MPa nitrogen for 3 times and then replaced with 3 MPa hydrogen for 3 times, hydrogen was filled to make the pressure 7 MPa. After the temperature was raised from room temperature to 450°C at a temperature rise rate of 10°C / min, the temperature was kept constant for 1 h, and then the temperature was rapidly lowered by using a blower. The results show that the n-hexane soluble yield is 68 wt.%.

[0046] Example 5

[0047] A preparation method of an Fe / Co composite oil-soluble catalyst: 100 g of kitchen waste red sesame oil and 62.50 g of formic acid were uniformly mixed, and then 87.50 g of a 30% hydrogen peroxide aqueous solution was added dropwise under stirring at 40°C. After stirring and reaction at the temperature for 5 h, 38.85 g of a sodium hydroxide solution (9.96 mol / L) was added under stirring to perform a saponification reaction. After reaction for 1.5 h under stirring, 28.71 g of iron chloride (5.18 mol / L) and 15.03 g of cobalt nitrate (3.63 mol / L) were added dropwise to perform a double decomposition reaction. After reaction for 0.5 h under stirring, the mixture was filtered and dried in a vacuum drying box at 75°C for 24 h to obtain a solid oil-soluble Fe / Co composite catalyst, wherein the molar ratio of Fe to Co is 1:1.

[0048] The oil-soluble Fe / Co composite catalyst prepared from the Shangwan coal sample (dry ash-free basis), sulfur, and tetrahydronaphthalene was mixed and added to a 100 mL high-pressure reaction kettle. The mass ratio of the Shangwan coal sample to tetrahydronaphthalene was 1:2; the molar ratio of sulfur to Fe+Ni was 2:1; and the addition amount of the oil-soluble Fe / Ni composite catalyst (based on the mass of active metals Fe+Ni) was 1 wt% of the Shangwan coal sample. After being replaced with 3 MPa nitrogen for 3 times and then replaced with 3 MPa hydrogen for 3 times, hydrogen was filled to make the pressure 7 MPa. After the temperature was raised from room temperature to 450°C at a temperature rise rate of 10°C / min, the temperature was kept constant for 1 h, and then the temperature was rapidly lowered by using a blower. The results show that the n-hexane soluble yield is 68 wt.%.

[0049] Example 6

[0050] A method for preparing an Fe-based oil-soluble catalyst: 100 g of kitchen waste walnut oil and 62.50 g of formic acid were mixed uniformly, and then 87.50 g of a 30% hydrogen peroxide aqueous solution was added dropwise under stirring at 30°C. After stirring at this temperature for 5 h, the mixture was heated and stirred to 60°C, and then 38.85 g of a sodium hydroxide solution (9.96 mol / L) was added for saponification reaction. After stirring for 1.5 h, 57.42 g of iron chloride (5.18 mol / L) was added dropwise for double decomposition reaction. After stirring for 0.5 h, the mixture was filtered and dried 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 tetrahydronaphthalene were mixed and added to a 100 mL high-pressure reaction kettle. The mass ratio of the Shangwan coal sample to tetrahydronaphthalene was 1:2, the molar ratio of sulfur to Fe was 2:1, and the addition amount of the oil-soluble Fe-based catalyst (based on the mass of active metal Fe) was 1 wt% of the Shangwan coal sample. After being replaced with 3 MPa nitrogen for 3 times and then replaced with 3 MPa hydrogen for 3 times, hydrogen was filled to make the pressure reach 7 MPa. After the temperature was raised from room temperature to 450°C at a heating rate of 10°C / min, the temperature was kept constant for 1 h, and then the temperature was rapidly lowered by using a blower. The results showed that the n-hexane soluble yield was 64 wt.%.

[0052] Example 7

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

[0054] Example 8

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

[0056] Example 9

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

[0058] Example 10

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

[0060] Comparative Example 1

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

[0062] Comparative Example 2

[0063] Shangwan coal sample (dry ash-free basis), analytical pure ferric oxide catalyst of Tianjin Beilian Fine Chemical Development Co., Ltd., sulfur and tetrahydronaphthalene were mixed and then added into a 100 mL high-pressure reactor. The mass ratio of the Shangwan coal sample and tetrahydronaphthalene was 1:2; the molar ratio of sulfur to Fe was 2:1; and the addition amount of the ferric oxide catalyst (based on the mass of active metal Fe) was 1 wt% of the Shangwan coal sample. After being replaced with 3 MPa nitrogen for 3 times and then replaced with 3 MPa hydrogen for 3 times, hydrogen was filled to make the pressure reach 7 MPa. After the temperature was raised from room temperature to 450℃ at a temperature raising rate of 10℃ / min, the temperature was kept constant for 1 h, and then the temperature was rapidly lowered by using a blower. The results show that the n-hexane soluble yield is 57 wt.%.

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

[0065] Comparative Example 3

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

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

[0068] Unless otherwise defined, all terms used in disclosing the application, which are known to one of ordinary skill in the art (SOT) are taken in their ordinary meaning.

[0069] The embodiments described herein are merely exemplary and are not intended to limit the scope of the application. Various other substitutions, changes and modifications can be suggested by those skilled in the art and it is intended that the application embrace all such changes and modifications within its scope.

Claims

1. A method for preparing an oil-soluble catalyst for the hydroconversion of coal and / or heavy oil, characterized in that, The method includes: mixing waste oil with formic acid, adding hydrogen peroxide aqueous solution dropwise while stirring at 30℃-40℃, stirring and reacting for 0.5-5h after the addition is complete, continuing to stir and heating to 40℃-80℃, adding alkaline solution, and reacting for 0.5-3h while stirring; then adding an inorganic salt solution of an active metal element dropwise, and reacting for 0.1-0.5h while stirring; filtering and drying the resulting mixture to obtain the solid oil-soluble catalyst, wherein the active metal element is selected from one or more of Fe, Ni, Mo, Co or W; The waste oil and formic acid are mixed at a mass ratio of 6-15:5; The waste oil includes waste oil from catering.

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

3. The method for preparing the oil-soluble catalyst for the hydroconversion of coal and / or heavy oil according to claim 2, characterized in that, The amount of the hydrogen peroxide aqueous solution used is 0.5-1 times the mass of the waste oil.

4. The method for preparing the oil-soluble catalyst for the hydroconversion of coal and / or heavy oil according to claim 1, characterized in that, The mass concentration of the hydrogen peroxide aqueous solution is 10%-50%.

5. The method for preparing the oil-soluble catalyst for the hydroconversion of coal and / or heavy oil according to claim 4, characterized in that, The mass concentration of the hydrogen peroxide aqueous solution is 25%-35%.

6. The method for preparing the oil-soluble catalyst for the hydroconversion of coal and / or heavy oil according to claim 1, characterized in that, The alkaline solution includes one or more of sodium hydroxide aqueous solution or potassium hydroxide aqueous solution; And / or, the mass concentration of the alkaline solution is 10%-50%.

7. The method for preparing the oil-soluble catalyst for the hydroconversion of coal and / or heavy oil according to claim 6, characterized in that, The mass concentration of the alkaline solution is 25%-35%.

8. The method for preparing the oil-soluble catalyst for the hydroconversion of coal and / or heavy oil according to claim 4, characterized in that, The mass ratio of the alkaline solution to the waste oil is 1:1-5.

9. The method for preparing the oil-soluble catalyst for the hydroconversion of coal and / or heavy oil according to claim 8, characterized in that, The mass ratio of the alkaline solution to the waste oil is 1:2-4.

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

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

12. The method for preparing an oil-soluble catalyst for the hydroconversion of coal and / or heavy oil according to any one of claims 1 to 11, characterized in that, The waste cooking oil includes vegetable oil.

13. The method for preparing the oil-soluble catalyst for the hydroconversion of coal and / or heavy oil according to claim 12, characterized in that, The vegetable oil contains unsaturated fatty acids.

14. The method for preparing the oil-soluble catalyst for the hydroconversion of coal and / or heavy oil according to claim 13, characterized in that, The vegetable oil includes oleic acid and linoleic acid.

15. The method for preparing the oil-soluble catalyst for the hydroconversion of coal and / or heavy oil according to claim 14, characterized in that, The vegetable oils include one or more selected from peanut oil, soybean oil, walnut oil, sunflower seed oil, flaxseed oil, rice bran oil, corn oil, jatropha oil, palm oil, tung oil, coconut oil, cottonseed oil, camellia seed oil, rapeseed oil, safflower seed oil, or peony seed oil.

16. An oil-soluble catalyst, said oil-soluble catalyst being prepared by any one of claims 1 to 15.

17. The application of the oil-soluble catalyst prepared by the method for preparing an oil-soluble catalyst for coal and / or heavy oil hydroconversion according to any one of claims 1 to 15, or the oil-soluble catalyst according to claim 16, in the hydroconversion of coal and / or heavy oil.

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