Selective nickel based hydrogenation catalyst and the preparation thereof

Abstract

A selective nickel-based hydrogenation catalyst and the preparation thereof, characterized in that: provided that the catalyst is weighed 100%, it comprises nickel oxide 14-20% as active component, lanthanum oxide and/or cerium oxide 2-8%, and VIB element oxide 1-8% as aids, 2-8% silica, 1-8% alkaline earth metal oxides, and alumina as the balance. The catalyst specific surface area is 60-150 m.sup.2/g, and the pore volume is 0.4-0.6 ml/g. The catalyst has good hydrogenation performance, especially impurity and colloid resistance and hydrogenation stability. The catalyst can be applied to the diolefin selective hydrogenation of medium or low-distillate oil, especially of the full-distillates pyrolysis gasoline.

Claims

1. A method for preparing a selective nickel-based hydrogenation catalyst, the method comprising: adding silica or its precursor and alkaline earth metal oxide or its precursor into an alumina carrier so as to form a first mixture; calcinating the first mixture at the temperature of 800-1100 C. for 3-6 hours to form a modified alumina carrier; adding soluble salts of nickel, rare earth element and VIB group element into water so as to form a solution; adjusting the pH of the solution to 4-5 following full dissolution of the soluble salts to form an impregnating solution; impregnating the modified alumina carrier with the impregnating solution to form a second mixture; after impregnating, drying the second mixture at the temperature of 40-120 C.; and after drying, calcinating the second mixture at the temperature of 350-450 C. for 3-6 hours, thereby obtaining the resultant catalyst, wherein the modified alumina carrier is prepared by: adding silica sol, nitric acid and water into alumina hydrate so as to form a third mixture; after kneading and extruding the third mixture, drying the third mixture at the temperature of 40-120 C.; after drying, calcinating the third mixture at the temperature of 300-600 C. for 4-6 hours so as to form a carrier; impregnating the carrier with an impregnating solution formed by adding alkaline earth metal oxide into water; after impregnating, drying the carrier at the temperature of 40-120 C.; and after drying, calcinating the carrier at the temperature of 800-1100 C. for 4-6 hours, thereby forming the modified alumina carrier.

2. The method according to claim 1, wherein the catalyst comprises a nickel oxide in the amount of 15-19%.

3. The method according to claim 1, wherein the catalyst comprises a lanthanum oxide and/or cerium oxide in the amount of 3-5%.

4. The method according to claim 1, wherein the catalyst comprises an alkaline earth metal selected from the group consisting of magnesium, strontium, and a mixture thereof.

5. The method according to claim 1, wherein the catalyst comprises an alkaline earth metal oxide in the amount of 2-5%.

6. The method according to claim 1, wherein said VIB group element is one or more selected from the group consisting of chromium, molybdenum and tungsten.

7. The method according to claim 1, wherein the VIB group element oxide in the catalyst is in the amount of 3-6%.

8. A method for preparing a selective nickel-based hydrogenation catalyst, the method comprising: adding silica or its precursor and alkaline earth metal oxide or its precursor into an alumina carrier so as to form a first mixture; calcinating the first mixture at the temperature of 800-1100 C. for 3-6 hours to form a modified alumina carrier; adding soluble salts of nickel, rare earth element and VIB group element into water so as to form a solution; adjusting the pH of the solution to 4-5 following full dissolution of the soluble salts to form an impregnating solution; impregnating the modified alumina carrier with the impregnating solution to form a second mixture; after impregnating, drying the second mixture at the temperature of 40-120 C.; and after drying, calcinating the second mixture at the temperature of 350-450 C. for 3-6 hours, thereby obtaining the resultant catalyst, wherein the resultant catalyst comprise alumina as a carrier, wherein based on the total weight of the catalyst, the catalyst comprises: 14-20% nickel oxide as an active component; 1-8% lanthanum oxide and/or cerium oxide; 1-8% VIB group element oxide as aids; 2-8% silica; and 1-8% alkaline earth metal oxide; wherein said catalyst has a specific surface area of 60-150 m.sup.2/g and a pore volume of 0.4-0.6 ml/g, and wherein the modified alumina carrier is prepared by: adding silica sol, nitric acid and water into alumina hydrate so as to form a third mixture; after kneading and extruding the third mixture, drying the third mixture at the temperature of 40-120 C.; after drying, calcinating the third mixture at the temperature of 300-600 C. for 4-6 hours so as to form a carrier; impregnating the carrier with an impregnating solution formed by adding alkaline earth metal oxide into water; after impregnating, drying the carrier at the temperature of 40-120 C.; and after drying, calcinating the carrier at the temperature of 800-1100 C. for 4-6 hours, thereby forming the modified alumina carrier.

9. The method according to claim 8, wherein the nickel oxide in the catalyst is in the amount of 15-19%.

10. The method according to claim 8, wherein the lanthanum oxide and/or cerium oxide in the catalyst is in the amount of 3-5%.

11. The method according to claim 8, wherein said alkaline earth metal is magnesium and/or strontium.

12. The method according to claim 8, wherein the alkaline earth metal oxide in the catalyst is in the amount of 2-5%.

13. The method according to claim 8, wherein said VIB group element is one or more selected from the group consisting of chromium, molybdenum and tungsten.

14. The method according to claim 8, wherein the VIE group element oxide in the catalyst is in the amount of 3-6%.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) Source of starting materials:

(2) Nickel Nitrate: available from Xi'an Chemical Reagent Factory;

(3) Magnesium nitrate and strontium nitrate: available from Shanghai Colloid Chemical Plant;

(4) Cerium nitrate and lanthanum nitrate: available from Shensheng Reagent Factory, Fufeng, Yixing, Jiangsu;

(5) alumina powder: available from Lanhua Xiangxin Additives Factory.

Example 1

(6) 140 ml water, 5 ml nitric acid (the content of which is 60%) and 16 ml silica sol (comprising 40% silica) are added to 300 g pseudo-boehmite alumina powder. After kneading and extruding, the formed alumina carrier is dried in air at 120 C., and then calcinated at 560 C. for 4 hours. 100 g calcinated carrier is impregnated with a solution form by dissolving 26 g magnesium nitrate into water, dried in air at 120 C., and calcinated at 1050 C. for 4 hours, thereby obtaining the modified Al.sub.2O.sub.3 carrier.

(7) 10 g nickel nitrate is added to 20 ml water with stirring. While stirring, 2.1 g cerium nitrate and 0.3 g ammonium molybdate are added. The pH of the solution is adjusted to 4. Then 10 g carrier is impregnated with the solution, aged for 12 hours, dried at 120 C., and calcinated at 400 C. for 4 hours, thereby obtaining the catalyst.

Comparative Example 1

(8) 140 ml water and 5 ml nitric acid (the content of which is 60%) are added to 300 g pseudo-boehmite alumina powder. After kneading and extruding, the formed alumina carrier is dried in air at 120 C., and then calcinated at 560 C. for 4 hours. 100 g calcinated carrier is impregnated with a solution formed by dissolving 16.7 g magnesium nitrate and 3 g strontium nitrate into water, dried in air at 120 C., and calcinated at 1050 C. for 4 hours, thereby obtaining the Al.sub.2O.sub.3 carrier.

(9) 10 g nickel nitrate is added to 20 ml water with stirring. While stirring, 2.1 g cerium nitrate and 0.3 g ammonium molybdate are added. The pH of the solution is adjusted to 4. Then 10 g carrier is impregnated with the solution, aged for 12 hours, dried at 120 C., and calcinated at 400 C. for 4 hours, thereby obtaining the catalyst.

Example 2

(10) 140 ml water, 5 ml nitric acid (the content of which is 60%) and 14 ml silica sol (comprising 40% silica) are added to 300 g pseudo-boehmite alumina powder. After kneading and extruding, the formed alumina carrier is dried in air at 120 C., and then calcinated at 460 C. for 4 hours. 100 g calcinated carrier is impregnated with a solution formed by dissolving 20 g magnesium nitrate and 3.5 g strontium nitrate into water, dried in air at 120 C., and calcinated at 1000 C. for 4 hours, thereby obtaining the Al.sub.2O.sub.3 carrier.

(11) 8.6 g nickel nitrate is added to 20 ml water with stirring. While stirring, 1.5 g lanthanum nitrate and 0.6 g ammonium tungstate are added. The pH of the solution is adjusted to 4. Then 10 g carrier is impregnated with the solution, aged for 12 hours, dried at 120 C., and calcinated at 350 C. for 4 hours, thereby obtaining the catalyst.

Comparative Example 2

(12) 140 ml water, 5 ml nitric acid (the content of which is 60%) and 14 ml silica sol (comprising 40% silica) are added to 300 g pseudo-boehmite alumina powder. After kneading and extruding, the formed alumina carrier is dried in air at 120 C., and calcinated at 1000 C. for 4 hours, thereby obtaining the Al.sub.2O.sub.3 carrier.

(13) 8.6 g nickel nitrate is added to 20 ml water with stirring. While stirring, 1.5 g lanthanum nitrate and 0.6 g ammonium tungstate are added. The pH of the solution is adjusted to 4. Then 10 g carrier is impregnated with the solution, aged for 12 hours, dried at 120 C., and calcinated at 350 C. for 4 hours, thereby obtaining the catalyst.

Example 3

(14) 140 ml water, 5 ml nitric acid (the content of which is 60%) and 9 ml silica sol (comprising 40% silica) are added to 300 g pseudo-boehmite alumina powder. After kneading and extruding, the formed alumina carrier is dried in air at 120 C., and then calcinated at 460 C. for 4 hours. 100 g calcinated carrier is impregnated with a solution formed by dissolving 15.5 g magnesium nitrate into water, dried in air at 120 C., and calcinated at 1030 C. for 4 hours, thereby obtaining the Al.sub.2O.sub.3 carrier.

(15) 7.9 g nickel nitrate is added to 20 ml water with stirring. While stirring, 0.63 g cerium nitrate, 0.62 g lanthanum nitrate and 0.5 g ammonium tungstate are added. The pH of the solution is adjusted to 4. Then 10 g carrier is impregnated with the solution, aged for 12 hours, dried at 120 C., and calcinated at 400 C. for 4 hours, thereby obtaining the catalyst.

Comparative Example 3

(16) 140 ml water is added to 300 g pseudo-boehmite alumina powder. After kneading and extruding, the formed alumina carrier is dried in air at 120 C., and calcinated at 1030 C. for 4 hours, thereby obtaining the Al.sub.2O.sub.3 carrier.

(17) 7.9 g nickel nitrate is added to 20 ml water with stirring. While stirring, 0.6 g ammonium molybdate is added. The pH of the solution is adjusted to 4. Then 10 g carrier is impregnated with the solution, aged for 12 hours, dried at 120 C., and calcinated at 400 C. for 4 hours, thereby obtaining the catalyst.

Example 4

(18) 140 ml water, 5 ml nitric acid (the content of which is 60%) and 12 ml silica sol (comprising 40% silica) are added to 300 g pseudo-boehmite alumina powder. After kneading and extruding, the formed alumina carrier is dried in air at 120 C., and then calcinated at 460 C. for 4 hours. 100 g calcinated carrier is impregnated with a solution formed by dissolving 5.8 g strontium nitrate into water, dried in air at 120 C., and calcinated at 1020 C. for 4 hours, thereby obtaining the Al.sub.2O.sub.3 carrier.

(19) 9.5 g nickel nitrate is added to 20 ml water with stirring. While stirring, 1.1 g cerium nitrate, 1.1 g lanthanum nitrate and 0.6 g potassium chromate are added. The pH of the solution is adjusted to 4. Then 10 g carrier is impregnated with the solution, aged for 12 hours, dried at 120 C., and calcinated at 350 C. for 4 hours, thereby obtaining the catalyst.

Comparative Example 4

(20) 140 ml water, 5 ml nitric acid (the content of which is 60%) and 12 ml silica sol (comprising 40% silica) are added to 300 g pseudo-boehmite alumina powder. After kneading and extruding, the formed alumina carrier is dried in air at 120 C., and then calcinated at 460 C. for 4 hours. 100 g calcinated carrier is impregnated with a solution formed by dissolving 21.6 g magnesium nitrate into water, dried in air at 120 C., and calcinated at 1020 C. for 4 hours, thereby obtaining the Al.sub.2O.sub.3 carrier.

(21) 9.5 g nickel nitrate is added to 20 ml water with stirring. While stirring, 1.1 g cerium nitrate is added. The pH of the solution is adjusted to 4. Then 10 g carrier is impregnated with the solution, aged for 12 hours, dried at 120 C., and calcinated at 350 C. for 4 hours, thereby obtaining the catalyst.

INDUSTRIAL APPLICABILITY

Analysis Method

(22) Distillation range of oil products: measured according to Petroleum Product Testing Method SYB-2110-60;

(23) Iodine value: measured according to IC1 method, expressed in g I.sub.2/100 g oil;

(24) Diolefin: measured according to maleic anhydride method, expressed in g I.sub.2/100 g oil;

(25) Arsenic content: measured by DV-4300 atomic emission spectroscopy;

(26) Sulfur content: measured by WK-2B microcoulometric detector;

(27) Colloid: measured according to Petroleum Product Testing Method SYB-2103-60.

(28) The full distillate pyrolysis gasoline is used as the starting materials, the properties of which are shown in Table 1. The catalysts of Examples 1, 2, 3 and 4 as well as Comparative Examples 1, 2, 3 and 4 are evaluated on 100 ml adiabatic bed hydrogenation apparatus. Firstly, the catalyst is reduced under hydrogen at the temperature of 350-400 C. for 10 hours. The temperature is lowered to 60 C. After the catalyst is inactivated by cyclohexane containing 1000 ppm dimethyl disulfide for 2 hours, the raw oil is added.

Reaction Condition

(29) Reaction pressure: 2.8 MPa,

(30) Intake temperature: room temperature 60 C.,

(31) Air speed of fresh raw oil: 3.5 h.sup.1,

(32) The volume ratio of hydrogen to oil: 200:1 (based on the fresh oil).

(33) The evaluation is carried out for 200 hours. And the iodine value and diolefin of the products are analyzed every 6 hours. The average data of the iodine value and diolefin of the product for each catalyst during the 200-hour evaluation are shown in Table 2.

(34) TABLE-US-00001 TABLE 1 Indexes of hydrogenation raw oil (C.sub.5-C.sub.9) Iodine Diolefin Sulfur Colloid Arsenic value 10.sup.2 10.sup.2 Distillation content 10.sup.2 Density content Color (g/g) (g/g) range ( C.) (ppm) (mg/ml) (g/ml) (ppb) Yellow 89.2 38.5 45-205 96 6.0 0.815 <20

(35) TABLE-US-00002 TABLE 2 Catalyst composition and average data of 200-hour evaluation in every example and comparative example Catalyst Comparative Comparative Comparative Comparative Example Example Example Example Example Example Example example Index 1 1 2 2 3 3 4 4 Product dioletin 10.sup.2 1.0 1.18 0.8 1.82 0.9 1.18 0.95 1.15 (g/g) Product iodine value 10.sup.2 41.3 44.2 39.8 45.3 40.2 42.6 40.5 41.8 (g/g) The colloid content after 6.1 5.9 5.8 7.5 6.2 8.6 6.5 6.8 200 hours reaction % Specific surface area of 93.78 88.02 105.3 108.9 88.26 87.29 95.84 104.93 the catalyst/m.sup.2 .Math. g.sup.1 Specific pore volume of 0.42 0.48 0.46 0.43 0.52 0.45 0.44 0.46 the catalyst/cm.sup.3 .Math. g.sup.1 Active Nickel oxide 18.8 18.8 16.6 16.6 15.6 16.1 17.9 18.9 component Silica 4.3 / 3.7 3.7 2.4 / 3.2 3.2 and aids Lanthanum / / 4.2 4.2 1.8 / 3.0 / content/wt % oxide Cerium oxide 6.1 6.1 / / 1.9 / 3.2 3.4 Magnesium 3.9 2.4 2.9 / 2.4 / / 3.3 oxide Strontium / 1.6 1.8 / / / 3.2 / oxide Molybdenum 1.7 1.7 / / / 3.9 / / oxide Tungsten oxide / / 3.8 3.8 3.3 / / / Chromium / / / / / / 2.3 / oxide

(36) 1000-hour long period evaluation is performed on the catalyst of Example 2. The evaluation was carried out on 100 ml adiabatic bed hydrogenation apparatus. Firstly, the catalyst is reduced under hydrogen at the temperature of 400-450 C. for 10 hours. The temperature is lowered to 60 C. After the catalyst is inactivated by cyclohexane containing 1000 ppm dimethyl disulfide for 3 hours, the raw oil is added.

(37) Reaction condition:

(38) Reaction pressure: 2.8 MPa,

(39) Intake temperature: room temperature 70 C.,

(40) Air speed of fresh raw oil: 2.8 h.sup.1,

(41) The volume ratio of hydrogen to oil: 200:1 (based on the fresh oil).

(42) The iodine value and diolefin of the product are analyzed every 12 hours. The average data during every 200 hours are taken. The indexes of hydrogenation raw oil (C.sub.5-C.sub.9) are shown in Table 3.

(43) TABLE-US-00003 TABLE 3 Indexes of hydrogenation raw oil (C.sub.5-C.sub.9) Iodine Diolefin Sulfur Colloid Arsenic value 10.sup.2 10.sup.2 Distillation content 10.sup.2 Density content Color (g/g) (g/g) range ( C.) (ppm) (mg/ml) (g/ml) (ppb) Yellow 88.5 39.5 45-205 86 7 0.815 26

(44) The results of evaluation are shown in Table 4. During the 1000-hour operation, the iodine value and diolefin value of the hydrogenation product remain at low level, which sufficiently indicates that the catalyst in Example 2 has good stability and hydrogenation activity.

(45) TABLE-US-00004 TABLE 4 1000-hour evaluation data for catalysts of Example 2 and Comparative Example 3 Hydrogenation product index Cumu- Catalyst of Comparative lative Catalyst of Example 2 Example 3 operation Diolefin Iodine Diolefin Iodine time 10.sup.2 value 10.sup.2 10.sup.2 value 10.sup.2 (h) (g/g) (g/g) (g/g) (g/g) 200 0.8 36.8 0.8 36.0 400 0.8 37.2 1.1 38.9 600 1.0 38.6 1.4 39.8 800 1.2 39.6 1.8 40.3 1000 1.4 40.2 2.5 43.6

(46) In summary, the hydrogenation catalyst according to the present invention has good hydrogenation performance, especially has impurity and colloid resistance as well as good hydrogenation stability. The catalyst can be applied to selective hydrogenation of diolefin unsaturated hydrocarbons, especially the first-stage selective hydrogenation process of full distillate pyrolysis gasoline.