Fe-based hydrogenation catalyst and use thereof

Abstract

The present invention relates to a Fe-based hydrogenation catalyst having Fe as a primary active metal component, and zinc and potassium as a first co-active metal component. The molar ratio of the primary active metal component to the first co-active metal component is 0.5-200:1. The Fe-based hydrogenation catalyst in present invention overcomes the problem of limiting to the active metal components as used over decades for the conventional hydrogenation catalyst, and thus has long-term values for industrial application.

Claims

1. A Fe-based hydrogenation catalyst, consisting of: Fe as a primary active metal component; zinc and potassium as a first co-active metal component, and a second co-active element component selected from titanium, zirconium, phosphorus, vanadium, cobalt, nickel, palladium and platinum, wherein, based on the total weight of the Fe-based hydrogenation catalyst, a total amount of the primary active metal component and co-active element components is 5-100%, with the balance being a binder or carrier, in terms of oxides, and wherein the co-active element components comprise the first co-active metal component and the second co-active element component, wherein the primary active metal component to the first co-active metal component has a molar ratio that is 0.5-200:1, wherein the molar ratio of the primary active metal component to the second co-active element component is 0.5-200:1.

2. The Fe-based hydrogenation catalyst according to claim 1, wherein the molar ratio of the primary active metal component to the first co-active metal component is 0.8-20:1.

3. The Fe-based hydrogenation catalyst according to claim 1, wherein, based on the total weight of the Fe-based hydrogenation catalyst, the total amount of the primary active metal component and the co-active element components is 20-70%, with the balance being a binder or carrier, in terms of oxides.

4. The Fe-based hydrogenation catalyst according to claim 3, wherein based on the total weight of the Fe-based hydrogenation catalyst, the total amount of the primary active metal component and co-active element components is 20-50%, with the balance being a binder or carrier, in terms of oxides.

5. The Fe-based hydrogenation catalyst according to claim 1, wherein the molar ratio of the primary active metal component to the second co-active element component is 5-100:1.

6. The Fe-based hydrogenation catalyst according to claim 1, which is prepared by an impregnation process, a coprecipitation process or a tableting process.

7. The Fe-based hydrogenation catalyst according to claim 6, wherein the impregnation process comprises steps of: dissolving a salt of the primary active metal component, a salt of the first co-active metal component and a salt of the second co-active metal component into deionized water to form an impregnation solution; adding the impregnation solution in a carrier to obtain a semi-finished catalyst product; and leaving the semi-finished catalyst product still in air for 2-24 hours, then baking it to dryness, and further calcinating it in air atmosphere at 200-800 C. for 2-8 h to obtain the Fe-based hydrogenation catalyst.

8. The Fe-based hydrogenation catalyst according to claim 7, wherein the carrier includes one of pyrite, pyrrhotite, ferric oxide, ferroferric oxide, alumina, silica, amorphous aluminosilicate, and zeolite molecular sieve, or combination of more than one members thereof.

9. The Fe-based hydrogenation catalyst according to claim 6, wherein the coprecipitation process comprises steps of: mixing uniformly an aqueous solution of a salt of the primary active metal component, a salt of the first co-active element component and a salt of the second co-active metal component with an aqueous solution of a precipitant; subsequently stirring and reacting the mixture in a water bath at 40-95 C. for 1-24 hours, and then leaving the resultant still for aging in a water bath at 40-95 C. for 2-48 hours to obtain a precipitate; subjecting the precipitate to filtration, water-washing and baking to dryness, to obtain a catalyst precursor; calcinating the catalyst precursor in air atmosphere at 200-800 C. for 2-8 hours to obtain a metal oxide; and mixing the metal oxide and a binder, and subjecting the mixture to a molding process to obtain the Fe-based hydrogenation catalyst.

10. The Fe-based hydrogenation catalyst according to claim 9, wherein the binder includes one of alumina, silica sol, alumina sol and water glass, or combination of more than one members thereof.

11. The Fe-based hydrogenation catalyst according to claim 9, wherein the precipitant includes one of NaOH, KOH, Na.sub.2CO.sub.3, K.sub.2CO.sub.3, Na.sub.2S, (NH.sub.4).sub.2S, urea and ammonia, or combination of more than one members thereof; and wherein the molar ratio of the precipitant to the total molar amount of primary active metal component, the first co-active metal component and the second co-active element component is 1-6:1.

12. The Fe-based hydrogenation catalyst according to claim 7, wherein the salt of the primary active metal component includes one of ferric nitrate, ferric sulfate, ferric chloride, and ferric phosphate, or combination of more than one members thereof; and the salt of the first co-active metal component includes one of nitrate, sulfate, chloride, and phosphate, or combination of more than one members thereof.

13. The Fe-based hydrogenation catalyst according to claim 6, wherein the tableting process comprises steps of: mixing uniformly a salt of the primary active metal component, a salt of the first co-active element component and a salt of the second co-active metal component; baking the mixture to dryness, and further calcinating the resultant in air atmosphere at 200-800 C. for 2-8 h to obtain a powder of oxides of the Fe-based hydrogenation catalyst; and adding a small amount of water to the powder of oxides of the Fe-based hydrogenation catalyst, and placing the resultant into a tablet machine for tableting, to obtain the Fe-based hydrogenation catalyst.

14. The Fe-based hydrogenation catalyst according to claim 7, wherein the salt of the second co-active element component includes one of nitrate, sulfate, chloride and phosphate, or combination of more than one members thereof.

15. A method, comprising subjecting the Fe-based hydrogenation catalyst of claim 1 to a sulfurization process prior to a hydrogenation process for one selected from the group consisting of straight-run gasoline, straight-run diesel, coker gasoline, coker diesel, catalytic cracking gasoline, catalytic cracking diesel, atmospheric residue oil, vacuum residue oil, coal tar and deasphalted oil and heavy oils extracted from oil sand or shale, and mixed oils thereof.

16. The method according to claim 15, wherein the sulfurization process having is carried out at a temperature of 200-450 C., a pressure of 0.1-10 MPa, a time duration of 2-48 hours, a liquid hourly space velocity of 0.1-20 h.sup.1 and a hydrogen-to-oil volume ratio of 100-800.

17. The method according to claim 16, wherein the sulfurization process is carried out at a temperature of 280-380 C., a pressure of 2-6 MPa, a time duration of 6-24 hours, a liquid hourly space velocity of 1-4 h.sup.1 and a hydrogen-to-oil volume ratio of 200-500.

18. The method according to claim 15, wherein the hydrogenation process is carried out at a temperature of 200-600 C., a pressure of 1-20 MPa, a liquid hourly space velocity of 0.1-10 h.sup.1 and a hydrogen-to-oil volume ratio of 100-2000.

19. The method according to claim 18, wherein the hydrogenation process has a temperature of 250-400 C., a pressure of 2-10 MPa, a liquid hourly space velocity of 0.5-8 h.sup.1 and a hydrogen-to-oil volume ratio of 200-1000.

Description

DETAILS DESCRIPTION OF THE DISCLOSURE

(1) Hereinafter, the technical solutions and effects are further explained in detail by reference to Examples, which should not be construed as limitations to the implementable scope of the present invention.

Example 1

(2) This Example provides a Fe-based hydrogenation catalyst for gasoline and diesel, which is prepared by using a impregnation process comprising steps of:

(3) dissolving 15.18 g of ferric nitrate, 3.65 g of zinc nitrate and 0.05 g of potassium nitrate into 10 mL of deionized water to formulate a impregnation solution;

(4) adding the impregnation solution dropwise into 10 g of an extrusion-molded alumina strip having a diameter of 1.5 mm to obtain a semi-finished catalyst product; and

(5) leaving the semi-finished catalyst product still in air for 20 hours, then baking it to dryness in an oven at 120 C., subsequently elevating the temperature at a rate of 5 C./min and calcinating it in air atmosphere at 500 C. for 4 hours, to obtain the Fe-based hydrogenation catalyst for gasoline and diesel, FZ-1.

(6) The catalyst FZ-1 is measured to have a total amount of 26% for oxide of FeZnK, based on the total weight of the catalyst FZ-1.

Example 2

(7) This Example provides a Fe-based hydrogenation catalyst for gasoline and diesel, which is prepared by using a coprecipitation process comprising steps of:

(8) dissolving 32.44 g of ferric chloride and 6.82 g of zinc chloride into 250 mL of deionized water to obtain an aqueous solution of ferric chloride and zinc chloride; dissolving 8 g of potassium hydroxide into 80 mL of deionized water to obtain a solution of potassium hydroxide; adding the solution of potassium hydroxide slowly into the aqueous solution of ferric chloride and zinc chloride while stirring;

(9) stirring and reacting the resultant for 4 hours in a water bath at 80 C., and then lowering the temperature to 60 C. and leaving it still for aging for 24 hour to obtain a precipitate;

(10) subjecting the precipitate to filtration before it cools, washing it by deionized water to pH of about 9 and baking it to dryness in an oven at 120 C., subsequently elevating the temperature at a rate of 5 C./min and calcinating it in air atmosphere at 500 C. for 2 hours to obtain an oxide of FeZnK; and

(11) mixing 4.5 g of the oxide of FeZnK, 10 g of pseudo-boehmite as a binder and 0.4 g of sesbania powder into a uniform powder, to obtain a mixed powder; dissolving 0.3 g of citric acid and 0.3 g of nitric acid into 10 mL deionized water to form a peptizer; adding the peptizer into the mixed powder and kneading them sufficiently to extrude them on a extruder into strips having a diameter of 1.5 mm; and baking the strips to dryness in an oven at 120 C. and then calcinating it in air atmosphere at 500 C. for 6 hours to obtain the Fe-based hydrogenation catalyst for gasoline and diesel, FZ-2.

(12) The catalyst FZ-2 is measured to have a total amount of 31% for oxide of FeZnK, based on the total weight of the catalyst FZ-2.

Example 3

(13) This Example provides a Fe-based hydrogenation catalyst for gasoline and diesel, which is prepared by using a impregnation process comprising steps of:

(14) dissolving 14.56 g of ferric sulfate, 4.78 g of zinc nitrate, 0.04 g of potassium nitrate and 0.08 g of phosphoric acid into 10 mL of deionized water to formulate a impregnation solution;

(15) adding the impregnation solution dropwise into 10 g of an extrusion-molded alumina strip having a diameter of 1.5 mm to obtain a semi-finished catalyst product; and

(16) leaving the semi-finished catalyst product still in air for 16 hours, then baking it to dryness in an oven at 120 C., subsequently elevating the temperature at a rate of 5 C./min and calcinating it in air atmosphere at 500 C. for 8 hours, to obtain the Fe-based hydrogenation catalyst for gasoline and diesel, FZ-3.

(17) The catalyst FZ-3 is measured to have a total amount of 30% for oxide of FeZnKP, based on the total weight of the catalyst FZ-3.

Example 4

(18) This Example provides a Fe-based hydrogenation catalyst for gasoline and diesel, which is prepared by using a impregnation process comprising steps of:

(19) dissolving 13.98 g of ferric phosphate, 6.65 g of zinc chloride, 0.09 g of potassium nitrate and 0.35 g of ammonium metavanadate into 10 mL of deionized water to formulate a impregnation solution;

(20) adding the impregnation solution dropwise into 10 g of an extrusion-molded alumina strip having a diameter of 1.5 mm to obtain a semi-finished catalyst product; and

(21) leaving the semi-finished catalyst product still in air for 2-24 hours, then baking it to dryness in an oven at 120 C., subsequently elevating the temperature at a rate of 5 C./min and calcinating it in air atmosphere at 500 C. for 4 hours, to obtain the Fe-based hydrogenation catalyst for gasoline and diesel, FZ-4.

(22) The catalyst FZ-4 is measured to have a total amount of 31% for oxide of FeZnKVP, based on the total weight of the catalyst FZ-4.

Example 5

(23) This Example provides a hydrogenation catalyst for gasoline and diesel, as a reference catalyst 1, which is prepared by a process comprising steps of:

(24) dissolving 4.74 g of ammonium metatungstate and 2.26 g of nickel nitrate into 10 mL of deionized water to formulate a impregnation solution;

(25) adding the impregnation solution dropwise into 10 g of an extrusion-molded alumina strip having a diameter of 1.5 mm to obtain a semi-finished catalyst product; and

(26) leaving the semi-finished catalyst product still in air for 2-24 hours, then baking it to dryness in an oven at 120 C., subsequently elevating the temperature at a rate of 5 C./min and calcinating it in air atmosphere at 500 C. for 4 hours, to obtain the reference catalyst 1.

(27) The reference catalyst 1 is measured to have a content of tungsten oxide of 27% and a content of nickel oxide of 4%, based on the total weight of the reference catalyst 1.

Example 6

(28) This Example provides a hydrogenation catalyst for gasoline and diesel, as a reference catalyst 2, which is prepared by a process comprising steps of:

(29) dissolving 20.05 g of ferric nitrate into 10 mL of deionized water to formulate a impregnation solution;

(30) adding the impregnation solution dropwise into 10 g of an extrusion-molded alumina strip having a diameter of 1.5 mm to obtain a semi-finished catalyst product; and

(31) leaving the semi-finished catalyst product still in air for 14 hours, then baking it to dryness in an oven at 120 C., subsequently elevating the temperature at a rate of 5 C./min and calcinating it in air atmosphere at 500 C. for 8 hours, to obtain the reference catalyst 2.

(32) The reference catalyst 2 is measured to have a content of Fe oxides of 31%, based on the total weight of the reference catalyst 2.

Example 7

(33) This Example provides a hydrogenation catalyst for gasoline and diesel, as a reference catalyst 3, which is prepared by a process comprising steps of:

(34) dissolving 14.56 g of ferric sulfate and 4.78 g of zinc nitrate into 10 mL of deionized water to formulate a impregnation solution;

(35) adding the impregnation solution dropwise into 10 g of an extrusion-molded alumina strip having a diameter of 1.5 mm to obtain a semi-finished catalyst product; and

(36) leaving the semi-finished catalyst product still in air for 24 hours, then baking it to dryness in an oven at 120 C., subsequently elevating the temperature at a rate of 5 C./min and calcinating it in air atmosphere at 500 C. for 2 hours, to obtain the reference catalyst 3.

(37) The reference catalyst 3 is measured to have a content of Fe oxide of 28%, based on the total weight of the reference catalyst 3.

Example 8

(38) This Example provides use of the catalysts in Examples 1-7 in the hydrogenation process of coker diesel.

(39) Each of the catalysts in Examples 1-7 is subjected to a sulfurization process before use, allowing it to have hydrogenation activity. The sulfurization process is a wet in-situ sulfurization process carried out by a 10 mL hydrogenation micro reactor at high-temperature and high-pressure, in which a wet sulfurization is applied, and after the sulfurization a hydrogenation reaction continues in the reactor without discharging the catalysts. The sulfurizing oil is a solution containing 5 wt % CS.sub.2 in n-decane. The sulfurization process has a temperature of 300 C., a time duration of 6 h, a pressure of 4 MPa, a liquid hourly space velocity of 1.5 h.sup.1, and a hydrogen-to-oil volume ratio of 300.

(40) The hydrogenation process in this Example is carried out using a 10 mL hydrogenation micro reactor at high-temperature and high-pressure, and a coker diesel from Daqing (Heilongjiang Province, China), having a specific gravity)(d.sub.4.sup.20) of 0.8196, a sulfur content of 1256 ppm and a total nitrogen content of 745 ppm, is used as raw material for evaluation. The raw material is pumped in using a plunger pump, and the oil sample after reaction is cooled by a higher separator, then collected and analyzed at a lower separator. The hydrogenation process has a temperature of 360 C., a pressure of 6 MPa, a liquid hourly space velocity of 1.0 h.sup.1, and a hydrogen-to-oil volume ratio of 800. The evaluation result of the catalyst obtained from the hydrogenation process is shown in Table 1 as below.

Example 9

(41) This Example provides use of the catalysts in Examples 1-7 in the hydrogenation process of catalytic cracking diesel.

(42) Each of the catalysts in Examples 1-7 is subjected to a sulfurization process before use, allowing it to have hydrogenation activity. The sulfurization process is a wet in-situ sulfurization process carried out by a 10 mL hydrogenation micro reactor at high-temperature and high-pressure, in which a wet sulfurization is applied, and after the sulfurization a hydrogenation reaction continues in the reactor without discharging the catalysts. The sulfurizing oil is a solution containing 5 wt % CS.sub.2 in n-decane. The sulfurization process has a temperature of 300 C., a time duration of 10 h, a pressure of 4 MPa, a liquid hourly space velocity of 1.5 h.sup.1, and a hydrogen-to-oil volume ratio of 300.

(43) The hydrogenation process in this Example is carried out using a 10 mL hydrogenation micro reactor at high-temperature and high-pressure, and a catalytic cracking diesel from Daqing (Heilongfiang Province, China), having a specific gravity (d.sub.4.sup.20) of 0.8796, a sulfur content of 890 ppm, a total nitrogen content of 920 ppm and a total aromatic hydrocarbon content of 55.2 v %, is used as raw material for evaluation. The raw material is pumped in using a plunger pump, and the oil sample after reaction is cooled by a higher separator, then collected and analyzed at a lower separator. The hydrogenation process has a temperature of 400 C., a pressure of 6 MPa, a liquid hourly space velocity of 1.0 h.sup.1, and a hydrogen-to-oil volume ratio of 800. The evaluation result of the catalysts obtained from the hydrogenation process is shown in Table 2 as below.

(44) TABLE-US-00001 TABLE 1 Catalysts HDS, % HDN, % FZ-1 83.0 69.4 FZ-2 81.2 71.2 FZ-3 84.5 70.8 FZ-4 87.2 72.1 Reference catalyst 1 98.5 85.6 Reference catalyst 2 10.1 5.0 Reference catalyst 3 70.2 68.0

(45) TABLE-US-00002 TABLE 2 Catalysts HDS, % HDN, % HDA, % FZ-1 81.0 61.6 45.4 FZ-2 78.7 59.2 43.1 FZ-3 82.3 60.4 44.9 FZ-4 84.6 58.1 43.2 Reference catalyst 1 93.9 72.3 58.8 Reference catalyst 2 8.4 5.1 6.2 Reference catalyst 3 65.2 55.1 40.1

Example 10

(46) This Example provides use of the catalysts in Examples 1-7 in the hydrogenation process of full-fraction FCC gasoline.

(47) Each of the catalysts in Examples 1-7 is subjected to a sulfurization process before use, allowing it to have hydrogenation activity. The sulfurization process is a wet in-situ sulfurization process carried out by a 10 mL hydrogenation micro reactor at high-temperature and high-pressure, in which a wet sulfurization is applied, and after the sulfurization a hydrogenation reaction continues in the reactor without discharging the catalysts. The sulfurizing oil is a solution containing 5 wt % CS.sub.2 in n-decane. The sulfurization process has a temperature of 300 C., a time duration of 6 h, a pressure of 2 MPa, a liquid hourly space velocity of 1.5 h.sup.1, and a hydrogen-to-oil volume ratio of 300.

(48) The hydrogenation process in this Example is carried out using a 10 mL hydrogenation micro reactor at high-temperature and high-pressure, and a full-fraction FCC gasoline, having a specific gravity (d.sub.4.sup.20) of 0.7296, a sulfur content of 470 ppm and a research octane number (RON) of 92.0, is used as raw material for evaluation. The raw material is pumped in using a plunger pump, and the oil sample after the reaction is cooled by a higher separator, then collected and analyzed at a lower separator. The hydrogenation process has a temperature of 280 C., a pressure of 4 MPa, a liquid hourly space velocity of 1.0 h.sup.1, and a hydrogen-to-oil volume ratio of 300. The evaluation result of the catalysts obtained from the hydrogenation process is shown in Table 3 as below.

(49) TABLE-US-00003 TABLE 3 Catalysts HDS, % RON Yield of gasoline, % FZ-1 80.5 91 99.1 FZ-2 77.2 91 99.2 FZ-3 81.5 92 98.3 FZ-4 82.1 90 97.2 Reference catalyst 1 94 90 99.3 Reference catalyst 2 12.3 92 99.0 Reference catalyst 3 62.1 92 98.1

(50) In above Examples, the methods for measurement and calculation of the HDS rate, HDN rate and HDA rate of the catalysts, and RON of oils and yield of gasoline are those well-known in the art.

(51) The results in Tables 1, 2 and 3 show that the Fe-based hydrogenation catalysts provided in the present invention has high hydro-desulfurization, -denitrification and -dearomatization activities, as compared with the reference catalysts. Moreover, when the Fe-based hydrogenation catalysts in the present invention are used in the hydrogenation of gasoline, it can cause little loss of the octane number of gasoline.

(52) The Fe-based hydrogenation catalysts provided in Examples of the present invention are characterized by incorporating more co-active element components. Moreover, as compared to the reference catalyst 2 in which no co-active element components are incorporated, the catalyst (reference catalyst 3) having zinc incorporated is improved in terms of its hydro-desulfurization, -denitrification and -dearomatization rate, by several to tens of times, and the incorporation of potassium can further improve the hydro-desulfurization activity of the catalyst (reference catalyst 3) having only zinc incorporated.

(53) Although the Fe-based hydrogenation catalysts provided in Examples of the present invention have a HDS, HDN and HDA rate slightly lower than those of the conventional supported NiW catalyst (reference catalyst 1), the primary active metal component and co-active element (metal) components as used in the Examples of the present invention have prices much lower than the nickel salt, cobalt salt, tungsten salt, molybdenum salt and so on as used in the conventional hydrogenation catalysts. Furthermore, the Fe-based hydrogenation catalyst provided in Examples of the present invention overcomes the problem of limiting to the active metal components as used over decades for the conventional hydrogenation catalyst for gasoline and diesel, thus has long-term values for industrial application.

Example 11

(54) This Example provides a carrier of Fe-based hydrogenation catalyst for heavy oils, which is prepared by a process comprising steps of:

(55) mixing uniformly 10 g of pseudo-boehmite powder and 0.3 g of sesbania powder to obtain a mixed powder;

(56) dissolving 0.3 g of dilute nitric acid and 0.3 g of citric acid into 20 mL of deionized water to obtain a mixed solution;

(57) dropping the mixed solution slowly into the mixed powder, mixing them uniformly to form a moldable body, and extruding it into a strip having a diameter of 1.2 mm on an extruder; and

(58) baking the strip to dry in an oven at 120 C., and then calcinating it in air atmosphere at 500 C. for 4 hours to obtain the catalyst carrier.

Example 12

(59) This Example provides a carrier of Fe-based hydrogenation catalyst for heavy oils, which is prepared by a process comprising steps of:

(60) mixing uniformly 7 g of pseudo-boehmite powder, 3 g of MCM-41 molecular sieve, and 0.3 g of sesbania powder to obtain a mixed powder;

(61) dissolving 0.3 g of dilute nitric acid and 0.3 g of citric acid into 20 mL of deionized water to obtain a mixed solution;

(62) dropping the mixed solution slowly into the mixed powder, mixing them uniformly to form a moldable body, and extruding it into a strip having a diameter of 1.2 mm on an extruder; and

(63) baking the strip to dry in an oven at 120 C., and then calcinating it in air atmosphere at 500 C. for 4 hours to obtain the catalyst carrier.

Example 13

(64) This Example provides a Fe-based hydrogenation catalyst for heavy oils, which is prepared by a process comprising steps of:

(65) mixing 29.52 g of ferric nitrate, 6.09 g of zinc nitrate and 0.15 g of potassium nitrate, and then dissolving the mixture into 20 mL of deionized water to form a impregnation solution;

(66) dropping the impregnation solution slowly into 10 g of the catalyst carrier in Example 11, and mixing them uniformly to obtain a semi-finished catalyst product; and

(67) leaving the semi-finished catalyst product still at room temperature for 4 hours, then baking it to dry in an oven at 120 C., subsequently calcinating it in air atmosphere at 500 C. for 4 hours, to obtain the Fe-based hydrogenation catalyst for heavy oils, C1.

(68) The Fe-based hydrogenation catalyst for heavy oils, C1, is measured to have a total amount of 40% for oxides of FeZnK and a balance of macroporous alumina, based on the total weight of the catalyst C1. The data for specific surface area, pore volume and average pore size of the Fe-based hydrogenation catalyst for heavy oils, C1, are shown in Table 5, wherein the methods for measurement and calculation of the specific surface area, pore volume and average pore size of the catalysts are those well-known in the art.

Example 14

(69) This Example provides a Fe-based hydrogenation catalyst for heavy oils, which is prepared by a process comprising steps of:

(70) mixing 25.30 g of ferric sulfate, 12.18 g of zinc chloride, 0.10 g of potassium sulfate and 1.05 g of zirconium nitrate, and then dissolving the mixture into 20 mL of deionized water to form a impregnation solution;

(71) adding the impregnation solution slowly into 10 g of the catalyst carrier in Example 12, and mixing them uniformly to obtain a semi-finished catalyst product; and

(72) leaving the semi-finished catalyst product still at room temperature for 4 hours, then baking it to dry in an oven at 120 C., subsequently calcinating it in air atmosphere at 500 C. for 4 hours, to obtain the Fe-based hydrogenation catalyst for heavy oils, C2.

(73) The Fe-based hydrogenation catalyst for heavy oils, C2, is measured to have a total amount of 40% for oxide of FeZnKZr and a balance of macroporous alumina and MCM-41, based on the total weight of the catalyst C2. The data for specific surface area, pore volume and average pore size of the Fe-based hydrogenation catalyst for heavy oils, C2, are shown in Table 5.

Example 15

(74) This Example provides a Fe-based hydrogenation catalyst for heavy oils, which is prepared by a process comprising steps of:

(75) mixing 18.26 g of ferric phosphate, 20.78 g of zinc sulfate, 0.20 g of potassium nitrate and 0.95 g of ammonium metavanadate, and then dissolving the mixture into 20 mL of deionized water to form a impregnation solution;

(76) adding the impregnation solution slowly into 10 g of the catalyst carrier in Example 12, and mixing them uniformly to obtain a semi-finished catalyst product; and

(77) leaving the semi-finished catalyst product still at room temperature for 8 hours, then baking it to dry in an oven at 120 C., subsequently calcinating it in air atmosphere at 500 C. for 6 hours, to obtain the Fe-based hydrogenation catalyst for heavy oils, C3.

(78) The Fe-based hydrogenation catalyst for heavy oils, C3, is measured to have a total amount of 40% for oxide of FeZnKZr and a balance of macroporous alumina and MCM-41, based on the total weight of the catalyst C3. The data for specific surface area, pore volume and average pore size of the Fe-based hydrogenation catalyst for heavy oils, C3, are shown in Table 5.

Example 16

(79) This Example provides a Fe-based hydrogenation catalyst for heavy oils, which is prepared by a process comprising steps of:

(80) mixing uniformly 19.80 g of ferric chloride, 14.18 g of zinc nitrate, 0.32 g of potassium sulfate and 1.00 g of titanyl sulfate, and then baking it in an oven at 120 C., subsequently calcinating it in air atmosphere at 500 C. for 4 hours, to obtain a powder of oxides of the Fe-based hydrogenation catalyst for heavy oils, C4; and

(81) adding 0.5 g of deionized water into the powder, mixing and then feeding them into a tablet machine for tabletting, to obtain the Fe-based hydrogenation catalyst for heavy oils, C4.

(82) The Fe-based hydrogenation catalyst for heavy oils, C4, has a total amount of FeZnKTi oxide of 100%, based on the total weight of the catalyst C4. The data for specific surface area, pore volume and average pore size of the Fe-based hydrogenation catalyst for heavy oils, C4, is shown in Table 5.

Example 17

(83) This Example provides a Fe-based hydrogenation catalyst for heavy oils, which is prepared by using a coprecipitation process comprising steps of:

(84) dissolving 32.44 g of ferric chloride and 6.82 g of zinc chloride into 250 mL of deionized water to obtain an aqueous solution of ferric chloride and zinc chloride; dissolving 8 g of potassium hydroxide into 80 mL of deionized water to obtain a solution of potassium hydroxide; adding the solution of potassium hydroxide slowly into the aqueous solution of ferric chloride and zinc chloride while stirring;

(85) stirring and reacting the mixture for 4 hours in a water bath at 80 C., and then lowering the temperature to 60 C. and leaving the resultant still for aging for 24 hour to obtain a precipitate;

(86) subjecting the precipitate to filtration when it is warm, washing by deionized water to pH of about 9 and baking it to dry in an oven at 120 C., subsequently elevating the temperature at a rate of 5 C./min and calcinating it in air atmosphere at 500 C. for 2 hours to obtain a FeZnK oxide; and

(87) mixing 6.0 g of the FeZnK oxide, 10 g of pseudo-boehmite as a binder and 0.4 g of sesbania powder into a uniform powder, to obtain a mixed powder; dissolving 0.3 g of citric acid and 0.3 g of nitric acid into deionized water to form a peptizer; adding the peptizer into the mixed powder and kneading them sufficiently to extrude them on a extruder into strips having a diameter of 1.5 mm; and baking the strips to dry in an oven at 120 C. and then calcinating it in air atmosphere at 500 C. for 8 hours to obtain the Fe-based hydrogenation catalyst for heavy oils, C5.

(88) The catalyst C5 is measured to have a total amount of 40% for the oxide of FeZnK, based on the total weight of the catalyst C5. The data for specific surface area, pore volume and average pore size of the Fe-based hydrogenation catalyst for heavy oils, C5, are shown in Table 5.

Example 18

(89) This Example provides a reference catalyst, which is prepared by a process comprising steps of:

(90) dissolving 33.73 g of ferric nitrate into 20 mL of deionized water to form a impregnation solution;

(91) dropping the impregnation solution slowly into 10 g of the catalyst carrier in Example 11, and mixing them uniformly to obtain a semi-finished catalyst product; and

(92) leaving the semi-finished catalyst product still at room temperature for 4 hours, then baking it to dry in an oven at 120 C., subsequently calcinating it in air atmosphere at 500 C. for 4 hours, to obtain the reference catalyst C6.

(93) The reference catalyst C6 is measured to have a total amount of 40% for Fe oxide and a balance of macroporous alumina, based on the total weight of the catalyst C6. The data for specific surface area, pore volume and average pore size of the reference catalyst C6 are shown in Table 5.

Example 19

(94) This Example provides a reference catalyst, which is prepared by a process comprising steps of:

(95) dissolving 27.62 g of ferric nitrate and 6.78 g of zinc nitrate into 20 mL of deionized water to form a impregnation solution;

(96) dropping the impregnation solution slowly into 10 g of the catalyst carrier in Example 12, and mixing them uniformly to obtain a semi-finished catalyst product; and

(97) leaving the semi-finished catalyst product still at room temperature for 4 hours, then baking it to dry in an oven at 120 C., subsequently calcinating it in air atmosphere at 500 C. for 4 hours, to obtain the reference catalyst C7.

(98) The reference catalyst C7 is measured to have a total amount of 40% for oxide of FeZn, and a balance of macroporous alumina and MCM-41, based on the total weight of the catalyst C7. The data for specific surface area, pore volume and average pore size of the reference catalyst C7 are shown in Table 5.

Example 20

(99) This Example provides a reference catalyst, which is prepared by a process comprising steps of:

(100) dissolving 2.27 g of ammonium metatungstate and 2.43 g of nickel nitrate into 20 mL of deionized water to form a impregnation solution;

(101) dropping the impregnation solution slowly into 10 g of the catalyst carrier in Example 12, and mixing them uniformly to obtain a semi-finished catalyst product; and

(102) leaving the semi-finished catalyst product still at room temperature for 4 hours, then baking it to dry in an oven at 120 C., subsequently calcinating it in air atmosphere at 500 C. for 4 hours, to obtain the reference catalyst C8.

(103) The reference catalyst C8 is measured to have a total amount of 20% for oxide of WNi, and a balance of macroporous alumina and MCM-41, based on the total weight of the catalyst C8. The data for specific surface area, pore volume and average pore size of the reference catalyst C8 are shown in Table 5.

Example 21

(104) This Example provides use of the catalysts in Examples 13-20 in the hydrogenation process of atmospheric residue oil.

(105) Each of the catalysts in Examples 13-20 is subjected to a sulfurization process before use, allowing it to have hydrogenation activity. The sulfurization process is a wet in-situ sulfurization process carried out by a 50 mL hydrogenation micro reactor at high-temperature and high-pressure, in which a wet sulfurization is applied, and after the sulfurization a hydrogenation reaction continues in the reactor without discharging the catalysts. The sulfurizing oil is a solution containing 5 wt % CS.sub.2 in n-decane. The sulfurization process has a temperature of 300 C., a time duration of 10 h, a pressure of 4 MPa, a liquid hourly space velocity of 1.5 h.sup.1, and a hydrogen-to-oil volume ratio of 300.

(106) The hydrogenation process in this Example is carried out using a 50 mL hydrogenation micro reactor at high-temperature and high-pressure, and an atmospheric residues of Saudi Arabian middle crude oils (of which the properties are shown in table 4) is used as raw material for evaluation. The raw material is pumped in using a plunger pump, and the oil sample after reaction is cooled by a higher separator, then collected and analyzed at a lower separator. The hydrogenation process has a temperature of 400 C., a pressure of 10 MPa, a liquid hourly space velocity of 1.0 h.sup.1, and a hydrogen-to-oil volume ratio of 1000. The evaluation result of the catalysts obtained from the hydrogenation process is shown in Table 5 as below.

(107) TABLE-US-00004 TABLE 4 atmospheric residues of Saudi Raw oils Arabian middle crude oils Density (20 C.), g/cm.sup.3 0.98 sulphur content, wt % 3.8 total nitrogen content, wt % 0.34

(108) TABLE-US-00005 TABLE 5 Catalysts C1 C2 C3 C4 C5 C6 C7 C8 Specific surface area, m.sup.2/g 170 315 325 71 102 324 173 357 Pore volume, cc/g 0.77 0.98 0.92 0.32 0.67 0.93 0.76 1.01 Average pore size, nm 11.9 9.0 11.4 8.0 8.2 9.4 12.3 11.1 HDS rate, % 50.4 54.1 55.0 55.2 49.8 7.9 47.1 67.0 HDN rate, % 31.8 32.9 34.1 33.8 31.0 5.1 30.5 40.2

Example 22

(109) This Example provides use of the catalysts in Examples 15, 16, 19 and 20 in the hydrogenation process of coker gas oil.

(110) Each of the catalysts in Examples 15, 16, 19 and 20 is subjected to a sulfurization process before use, allowing it to have better hydrogenation effect. The sulfurization process is a wet in-situ sulfurization process carried out by a 50 mL hydrogenation micro reactor at high-temperature and high-pressure, in which a wet sulfurization is applied and after the sulfurization a hydrogenation reaction continues in the reactor without discharging the catalysts. The sulfurizing oil is a solution containing 5 wt % CS.sub.2 in n-decane. The sulfurization process has a temperature of 400 C., a time duration of 8 h, a pressure of 5 MPa, a liquid hourly space velocity of 1.5 h.sup.1, and a hydrogen-to-oil volume ratio of 300.

(111) The hydrogenation process in this Example is carried out using a 50 mL hydrogenation micro reactor at high-temperature and high-pressure, and a coker gas oil from Dagang (Tianjin, China), having a sulphur content of 0.253 wt % and a total nitrogen content of 0.51 wt %, is used as raw material for evaluation. The raw material is pumped in using a plunger pump, and the oil sample after reaction is cooled by a higher separator, then collected and analyzed at a lower separator. The hydrogenation process has a temperature of 360 C., a pressure of 6 MPa, a liquid hourly space velocity of 1.5 h.sup.1, and a hydrogen-to-oil volume ratio of 500.

(112) The evaluation result of the catalysts obtained from the hydrogenation process is shown in Table 6 as below.

(113) TABLE-US-00006 TABLE 6 Catalysts C3 C4 C7 C8 HDS rate, % 39.2 39.6 32.1 48.7 HDN rate, % 30.1 31.2 30.3 36.0

Example 23

(114) This Example provides use of the catalysts in Examples 15, 16, 19 and 20 in the hydrogenation process of vacuum residue oil.

(115) Each of the catalysts in Examples 15, 16, 19 and 20 is subjected to a sulfurization process before use, allowing it to have better hydrogenation effect. The sulfurization process is a wet in-situ sulfurization process carried out by a 50 mL hydrogenation micro reactor at high-temperature and high-pressure, in which a wet sulfurization is applied and after the sulfurization a hydrogenation reaction continues in the reactor without discharging the catalysts. The sulfurizing oil is a solution containing 5 wt % CS.sub.2 in n-decane. The sulfurization process has a temperature of 360 C., a time duration of 12 h, a pressure of 4 MPa, a liquid hourly space velocity of 2 h.sup.1, and a hydrogen-to-oil volume ratio of 300.

(116) The hydrogenation process in this Example is carried out using a 50 mL hydrogenation micro reactor at high-temperature and high-pressure, and a vacuum residues of Saudi Arabian middle crude oils (of which the properties are shown in table 7) is used as raw material for evaluation. The raw material is pumped in using a plunger pump, and the oil sample after reaction is cooled by a higher separator, then collected and analyzed at a lower separator. The hydrogenation process has a temperature of 360 C., a pressure of 8 MPa, a liquid hourly space velocity of 1 h.sup.1, and a hydrogen-to-oil volume ratio of 800.

(117) The evaluation result of the catalysts obtained from the hydrogenation process is shown in Table 8 as below.

(118) TABLE-US-00007 TABLE 7 vacuum residues of Saudi Raw oils Arabian middle crude oils Density (20 C.), g/cm.sup.3 1.0220 Ni, ppm 60 V, ppm 186

(119) TABLE-US-00008 TABLE 8 Catalysts C3 C4 C7 C8 Total demetalization (Ni and V) rate, % 78 81 80 92

(120) The results in Tables 5, 6 and 8 shows that the Fe-based hydrogenation catalysts for heavy oils in Examples of the present invention has very high hydro-desulfurization, -denitrification and -dearomatization activities for heavy oils. The Fe-based hydrogenation catalysts in Examples of the present invention are characterized by incorporating co-active element (metal) components. Moreover, as compared with the reference catalyst C6 in which no co-active element (metal) components are incorporated, the catalyst having zinc incorporated (reference catalyst C7) is improved in terms of its hydro-desulfurization rate, by several times, and the incorporation of potassium can further improve the hydro-desulfurization activity of the catalyst (reference catalyst C7) having only zinc incorporated.

(121) Although the Fe-based hydrogenation catalysts provided in Examples of the present invention have a HDS, HDN and HDA rate slightly lower than those of the conventional supported NiW catalyst (reference catalyst C8), the primary active metal component and co-active metal components as used in the Examples of the present invention have prices much lower than the nickel salt, cobalt salt, tungsten salt, molybdenum salt and so on as used in the conventional hydrogenation catalysts. Furthermore, the Fe-based hydrogenation catalyst in Examples of the present invention overcomes the problem of limiting to the active metal components as used over decades for the conventional hydrogenation catalysts, thus has important values for theoretical study and industrial application.