Carrier and catalyst for selectively synthesizing kerosene fraction from syngas, and method for preparing the same

Abstract

A carrier for selectively synthesizing kerosene fraction from syngas, the carrier including the following components in parts by weight: 5-50 parts of mesoporous zirconia (ZrO.sub.2), 10-55 parts of a silicoaluminophosphate (SAPO) molecular sieve, 5-50 parts of modified mesoporous molecular sieve Al-SBA-16, 1-3 parts of sesbania gum powder, and 10-70 parts of alumina A catalyst includes a soluble cobalt salt and the aforesaid carrier. The soluble cobalt salt is loaded on the surface of the carrier.

Claims

1. A carrier, comprising the following components in parts by weight: 5-50 parts of mesoporous zirconia (ZrO.sub.2), 10-55 parts of a silicoaluminophosphate (SAPO) molecular sieve, 5-50 parts of modified mesoporous molecular sieve Al-SBA-16, 1-3 parts of sesbania gum powder, and 10-70 parts of alumina.

2. The carrier of claim 1, comprising the following components in parts by weight: 10-30 parts of the mesoporous zirconia, 25-45 parts of the silicoaluminophosphate molecular sieve, 10-30 parts of the modified Al-SBA-16, 1-3 parts of the sesbania gum powder, and 30-55 parts of the alumina.

3. The carrier of claim 2, comprising the following components in parts by weight: 20 parts of the mesoporous zirconia, 30 parts of the silicoaluminophosphate molecular sieve, 25 parts of the modified Al-SBA-16, 1 part of the sesbania gum powder, and 30 parts of the alumina.

4. The carrier of claim 1, wherein the modified Al-SBA-16 comprises SBA-16 and aluminum triethoxide (Al(OC.sub.2H.sub.7).sub.3), in which a weight ratio of SBA-16 to aluminum triethoxide is 1:3.0-4.5.

5. The carrier of claim 3, wherein the modified Al-SBA-16 comprises SBA-16 and aluminum triethoxide (Al(OC.sub.2H.sub.7).sub.3), in which a weight ratio of SBA-16 to aluminum triethoxide is 1:3.0-4.5.

6. The carrier of claim 1, wherein a molar ratio n of silicon to aluminum in the modified Al-SBA-16 is between 5 and 55, a Br?nsted acid (B acid) content thereof is 39-92 ?mol.Math.g.sup.?1, a Lewis acid (L acid) content thereof is 71-105 ?mol.Math.g.sup.?1, and a Na.sub.2O content thereof is ?0.1 wt. %.

7. The carrier of claim 3, wherein a molar ratio n of silicon to aluminum in the modified Al-SBA-16 is between 5 and 55, a Br?nsted acid (B acid) content thereof is 39-92 ?mol.Math.g.sup.?1, a Lewis acid (L acid) content thereof is 71-105 ?mol.Math.g.sup.?1, and a Na.sub.2O content thereof is ?0.1 wt. %.

8. The carrier of claim 6, wherein the molar ratio n of silicon to aluminum in the modified Al-SBA-16 is between 10 and 55, a specific surface area is 550-930 m.sup.2.Math.g.sup.?1, an average pore size is 4.0-7.5 nm, and a total pore volume is 0.45-0.70 cm.sup.3.Math.g.sup.?1.

9. The carrier of claim 7, wherein the molar ratio n of silicon to aluminum in the modified Al-SBA-16 is between 10 and 55, a specific surface area is 550-930 m.sup.2.Math.g.sup.?1, an average pore size is 4.0-7.5 nm, and a total pore volume is 0.45-0.70 cm.sup.3.Math.g.sup.?1.

10. The carrier of claim 1, wherein the modified mesoporous molecular sieve Al-SBA-16 is prepared as follows: 1) weighing SBA-16 and aluminum triethoxide according to an aforesaid weight ratio, and dividing the aluminum triethoxide into two equal portions for use; 2) adding SBA-16 to n-hexane, and uniformly stirring at room temperature, to obtain a mixed solution; adding one portion of the aluminum triethoxide to n-hexane, and stirring at room temperature until the aluminum triethoxide is dissolved; and adding the aluminum triethoxide dissolved in the n-hexane to the mixed solution, and stirring overnight at room temperature, to obtain a sample solution; 3) transferring the sample solution obtained in 2) to a Buchner funnel, washing with n-hexane, and suctioning; and repeating the washing and suctioning operations 2 to 4 times, to obtain a primary filter cake; 4) adding the primary filter cake to n-hexane, and uniformly stiffing at room temperature; adding another portion of the aluminum triethoxide; stirring overnight at room temperature, transferring to a Buchner funnel, washing with n-hexane, and suctioning; and repeating the washing and suctioning operations 2 to 4 times, to obtain a secondary filter cake; and 5) baking the secondary filter cake at 500-650? C. for 6-10 h, to obtain modified Al-SBA-16.

11. The carrier of claim 1, wherein the mesoporous zirconia has a specific surface area of 190-350 m.sup.2.Math.g.sup.?1, an average pore size of 5.0-8.5 nm, and a total pore volume of 0.40-0.55 cm.sup.3.Math.g.sup.?1.

12. The carrier of claim 1, wherein the silicoaluminophosphate molecular sieve has a total acid content of 0.1-0.35 mmol NH.sub.3.Math.g.sup.?1; a molar ratio of silicon to aluminum of 0-1.0; a specific surface area of ?150 m.sup.2.Math.g.sup.?1, a Na.sub.2O content of ?0.2 wt. %, and a total pore volume of 0.10-0.30 cm.sup.3.Math.g.sup.?1.

13. The carrier of claim 12, wherein the silicoaluminophosphate molecular sieve has a molar ratio of silicon to aluminum of 0.21-0.38, a specific surface area of ?180 m.sup.2.Math.g.sup.?1, a Na.sub.2O content of ?0.2 wt. %, and a total pore volume of 0.10-0.30 cm.sup.3.Math.g.sup.?1; or the silicoaluminophosphate molecular sieve has a molar ratio of silicon to aluminum of 0-1.0, a specific surface area of ?150 m.sup.2.Math.g.sup.?1, a Na.sub.2O content of ?0.2 wt. %, and a total pore volume of 0.13-0.26 cm.sup.3.Math.g.sup.?1.

14. A method for preparing a carrier, the method comprising: 1) separately weighing out SBA-16 and aluminum triethoxide according to a weight ratio 1:3.0-4.5, and dividing the aluminum triethoxide into two equal portions; 2) adding the SBA-16 to n-hexane, and uniformly stiffing at room temperature, to obtain a mixed solution; adding one portion of the aluminum triethoxide to n-hexane, and stiffing at room temperature until the aluminum triethoxide is dissolved; and adding the aluminum triethoxide dissolved in the n-hexane to the mixed solution, and stiffing overnight at room temperature, to obtain a sample solution; 3) transferring the sample solution obtained in 2) to a Buchner funnel, washing with n-hexane, and suctioning; and repeating the washing and suctioning operations 2 to 4 times, to obtain a primary filter cake; 4) adding the primary filter cake to n-hexane, and stiffing at room temperature; adding another portion of the aluminum triethoxide; stirring overnight at room temperature, transferring to a Buchner funnel, washing with n-hexane, and suctioning; and repeating the washing and suctioning operations 2 to 4 times, to obtain a secondary filter cake; 5) baking the secondary filter cake at 500-650? C. for 6-10 h, to obtain modified Al-SBA-16 for use; 6) uniformly kneading microporous alumina with a dilute nitric acid solution at a weight ratio of 1:0.5-1.5, to prepare a viscous paste for use, in which the concentration of the dilute nitric acid solution is 5-20 wt. %; and 7) weighing, in parts by weight, 5-50 parts of mesoporous zirconia, 10-55 parts of the silicoaluminophosphate molecular sieve, 5-50 parts of modified Al-SBA-16, 1-3 parts of sesbania gum powder and 10-70 parts of the viscous paste based on alumina; and uniformly mixing aforesaid components, rolling, extrusion molding, drying for 6-12 h at 90-120? C., then baking for 4-10 h in air at 500-600? C., and cooling to room temperature to obtain the carrier.

15. The method of claim 14, wherein the carrier is in the shape of a cylindrical strip, a clover or a four-leaf clover; the carrier in the shape of a cylindrical strip has a particle size of 1.2-1.6 mm, and a length of 5-10 mm; and the carrier in the shape of a clover or a four-leaf clover has a distance between two leaves of 1.1-1.8 mm, and a length of 5-10 mm.

16. A catalyst, comprising a soluble cobalt salt and a carrier of claim 1, the soluble cobalt salt being loaded on a surface of the carrier.

17. The catalyst of claim 16, wherein the soluble cobalt salt accounts for 5-20 wt. % of the catalyst.

18. The catalyst of claim 16, wherein the soluble cobalt salt is cobalt nitrate, cobalt acetate or carbonyl cobalt.

19. The catalyst of claim 17, wherein the soluble cobalt salt is cobalt nitrate, cobalt acetate or carbonyl cobalt.

20. A method for preparing the catalyst of claim 16, comprising: impregnating the carrier with an aqueous solution containing the soluble cobalt salt by iso-volume impregnation, aging the carrier overnight at room temperature, then drying for 4-12 h at 90-120? C. under normal pressure, baking for 4-10 h in air at 500-600? C. and cooling to room temperature to obtain the catalyst.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

(1) For a better explanation of the present disclosure, the main disclosure of the present disclosure is further described below with reference to specific embodiments. However, the present disclosure is not limited to the following embodiments.

(2) Preparation of Raw Materials Necessitated in the Carrier of the Present Disclosure

(3) I. Preparation of Modified Al-SBA-16

(4) 1. Preparation of Modified Al-SBA-16 (5)

(5) 1). 30 g of SBA-16 was weighed, added to 100 mL of n-hexane, and stirred for 2 h at room temperature.

(6) 2). 45 g of Al(OC.sub.2H.sub.7).sub.3 was weighed, added to 100 mL of n-hexane, and stirred at room temperature until it was dissolved. Then the solution of Al (OC.sub.2H.sub.7).sub.3 in n-hexane was added to a beaker containing SBA-16, and stirred overnight at room temperature.

(7) 3). The resulting sample was transferred to a Buchner funnel, washed with 50 mL of n-hexane, and suctioned. The process was repeated 3 times, to obtain a primary filter cake.

(8) 4). The primary filter cake was transferred to a beaker, and then 100 mL of n-hexane was added and stirred for 1 h at room temperature. Then, 45 g of Al (OC.sub.2H.sub.7).sub.3 was added and stirred overnight at room temperature. The filter cake was transferred to a Buchner funnel, washed with 50 mL of n-hexane, and suctioned. The process was repeated 3 times. Finally, the resulting secondary filter cake was baked for 10 h at 550? C., to obtain modified Al-SBA-16 (5) for use.

(9) 2. Preparation of Modified Al-SBA-16 (10)

(10) 1). 30 g of SBA-16 was weighed, added to 100 mL of n-hexane, and stirred for 3 h at room temperature.

(11) 2). 41 g of Al(OC.sub.2H.sub.7).sub.3 was weighed, added to 100 mL of n-hexane, and stirred at room temperature until it was dissolved. Then the solution of Al (OC.sub.2H.sub.7).sub.3 in n-hexane was added to a beaker containing SBA-16, and stirred overnight at room temperature.

(12) 3). The resulting sample was transferred to a Buchner funnel, washed with 50 mL of n-hexane, and suctioned. The process was repeated 3 times, to obtain a primary filter cake.

(13) 4). The primary filter cake was transferred to a beaker, and then 100 mL of n-hexane was added and stirred for 1.5 h at room temperature. Then, 41 g of Al (OC.sub.2H.sub.7).sub.3 was added and stirred overnight at room temperature. The filter cake was transferred to a Buchner funnel, washed with 50 mL of n-hexane, and suctioned. The process was repeated 3 times. Finally, the resulting secondary filter cake was baked for 8 h at 550? C., to obtain modified Al-SBA-16 (10) for use.

(14) 3. Preparation of Modified Al-SBA-16 (20)

(15) 1). 30 g of SBA-16 was weighed, added to 100 mL of n-hexane, and stirred for 4 h at room temperature.

(16) 2). 37 g of Al(OC.sub.2H.sub.7).sub.3 was weighed, added to 100 mL of n-hexane, and stirred at room temperature until it was dissolved. Then the solution of Al (OC.sub.2H.sub.7).sub.3 in n-hexane was added to a beaker containing SBA-16, and stirred overnight at room temperature.

(17) 3). The resulting sample was transferred to a Buchner funnel, washed with 50 mL of n-hexane, and suctioned. The process was repeated 3 times, to obtain a primary filter cake.

(18) 4). The primary filter cake was transferred to a beaker, and then 100 mL of n-hexane was added and stirred for 2 h at room temperature. Then, 37 g of Al (OC.sub.2H.sub.7).sub.3 was added and stirred overnight at room temperature. The filter cake was transferred to a Buchner funnel, washed with 50 mL of n-hexane, and suctioned. The process was repeated 3 times. Finally, the resulting secondary filter cake was baked for 6 h at 580? C., to obtain modified Al-SBA-16 (20) for use.

(19) 4. Preparation of Modified Al-SBA-16 (25)

(20) 1). 30 g of SBA-16 was weighed, added to 100 mL of n-hexane, and stirred for 4 h at room temperature.

(21) 2). 35 g of Al(OC.sub.2H.sub.7).sub.3 was weighed, added to 100 mL of n-hexane, and stirred at room temperature until it was dissolved. Then the solution of Al (OC.sub.2H.sub.7).sub.3 in n-hexane was added to a beaker containing SBA-16, and stirred overnight at room temperature.

(22) 3). The resulting sample was transferred to a Buchner funnel, washed with 50 mL of n-hexane, and suctioned. The process was repeated 3 times, to obtain a primary filter cake.

(23) 4). The primary filter cake was transferred to a beaker, and then 100 mL of n-hexane was added and stirred for 2 h at room temperature. Then, 35 g of Al (OC.sub.2H.sub.7).sub.3 was added and stirred overnight at room temperature. The filter cake was transferred to a Buchner funnel, washed with 50 mL of n-hexane, and suctioned. The process was repeated 3 times. Finally, the resulting secondary filter cake was baked for 6 h at 580? C., to obtain modified Al-SBA-16 (25) for use.

(24) 5. Preparation of Modified Al-SBA-16 (40)

(25) 1). 30 g of SBA-16 was weighed, added to 100 mL of n-hexane, and stirred for 4.5 h at room temperature.

(26) 2). 33 g of Al(OC.sub.2H.sub.7).sub.3 was weighed, added to 100 mL of n-hexane, and stirred at room temperature until it was dissolved. Then the solution of Al (OC.sub.2H.sub.7).sub.3 in n-hexane was added to a beaker containing SBA-16, and stirred overnight at room temperature.

(27) 3). The resulting sample was transferred to a Buchner funnel, washed with 50 mL of n-hexane, and suctioned. The process was repeated 3 times, to obtain a primary filter cake.

(28) 4). The primary filter cake was transferred to a beaker, and then 100 mL of n-hexane was added and stirred for 2.5 h at room temperature. Then, 33 g of Al (OC.sub.2H.sub.7).sub.3 was added and stirred overnight at room temperature. The filter cake was transferred to a Buchner funnel, washed with 50 mL of n-hexane, and suctioned. The process was repeated 3 times. Finally, the resulting secondary filter cake was baked for 6 h at 600? C., to obtain modified Al-SBA-16 (40) for use.

(29) 6. Preparation of Modified Al-SBA-16 (55)

(30) 1). 30 g of SBA-16 was weighed, added to 100 mL of n-hexane, and stirred for 5 h at room temperature.

(31) 2). 30 g of Al(OC.sub.2H.sub.7).sub.3 was weighed, added to 100 mL of n-hexane, and stirred at room temperature until it was dissolved. Then the solution of Al (OC.sub.2H.sub.7).sub.3 in n-hexane was added to a beaker containing SBA-16, and stirred overnight at room temperature.

(32) 3). The resulting sample was transferred to a Buchner funnel, washed with 50 mL of n-hexane, and suctioned. The process was repeated 3 times. Then the filter cake was transferred to a beaker, washed with 100 mL of n-hexane, and stirred for 3 h at room temperature. Thereafter, 30 g of Al(OC.sub.2H.sub.7).sub.3 was added, stirred overnight at room temperature to obtain a primary filter cake.

(33) 4). The primary filter cake was transferred to a Buchner funnel, washed with 50 mL of n-hexane, and suctioned. The process was repeated 3 times. Finally, the resulting secondary filter cake was baked for 6 h at 650? C., to obtain modified Al-SBA-16 (55) for use.

(34) II. Preparation of a Viscous Paste of Alumina

(35) Microporous alumina was kneaded with a dilute nitric acid solution at a weight ratio of 1:0.5-1.5, in which the concentration of the dilute nitric acid solution was 5-20 wt. %.

(36) In an industrialized operation, a preferred solution that follows is adopted.

(37) 500 g of dry microporous alumina powder was weighed and added to a feed tank of a kneader. 750 mL of 8 wt. % dilute nitric acid was slowly added to the feed tank. The kneader was started, and the materials were kneaded uniformly, to form a viscous paste for use.

(38) III. Selection of Silicoaluminophosphate Molecular Sieve

(39) The silicoaluminophosphate molecular sieve is commercially available, and the SPAO-11 molecular sieve, the SPAO-31 molecular sieve, or a mixture of the SPAO-11 and SPAO-31 molecular sieve is used. The SPAO-11 has a molar ratio of silicon to aluminum of 0.21-0.38, a specific surface area of ?180 m.sup.2.Math.g.sup.?1, a Na.sub.2O content of ?0.2 wt. %, and a total pore volume of 0.10-0.30 cm.sup.3.Math.g.sup.?1; and the SPAO-31 has a molar ratio of silicon to aluminum of 0-1.0, a specific surface area of ?150 m.sup.2.Math.g.sup.?1, a Na.sub.2O content of ?0.2 wt. %, and a total pore volume of 0.13-0.26 cm.sup.3.Math.g.sup.?1.

(40) Other raw materials used in the present disclosure are all commercially available.

(41) A carrier for selectively synthesizing a high-quality kerosene fraction from syngas was prepared with the above raw materials through a method as follows.

(42) 5-50% by weight (wt. %) of mesoporous zirconia, 10-55 wt. % of the silicoaluminophosphate molecular sieve, 5-50 wt. % of modified Al-SBA-16, 1-3 wt. % of sesbania gum powder and 10-70 wt. % of a binder were uniformly mixed, rolled, extrusion molded, dried for 6-12 h at 90-120? C., and then baked for 4-10 h in air at 500-600? C., and cooled to room temperature to obtain a carrier.

(43) In connection with the above method, the formulation in industrial production is shown in Table 1 below.

(44) TABLE-US-00001 TABLE 1 Example (g) Raw material 1 2 3 4 5 6 7 8 9 10 11 12 Mesoporous zirconia 15 15 10 10 30 30 20 20 5 50 15 5 Silicoaluminophosphate SPAO-11 25 25 45 45 10 10 30 30 15 10 Molecular sieve SPAO-31 55 10 10 Modified Al-SBA-16 5 (n) 10 (n) 10 (n) 5 15 20 (n) 10 5 30 55 25 (n) 20 30 (n) 20 40 (n) 30 55 (n) 20 5 Sesbania gum powder 1 1 1 1 1 1 1 1 2 3 1 2 Viscous paste (alumina) 167 167 133 133 100 100 100 100 67 34 233 100 (50) (50) (40) (40) (30) (30) (30) (30) (20) (10) (70) (30)

(45) Optimized reaction conditions are shown in Table 2.

(46) TABLE-US-00002 TABLE 2 Drying Drying Baking Baking temperature time temperature time Example (? C.) (h) (? C.) (h) 1 90 12 500 10 2 110 10 550 8 3 90 12 500 8 4 110 10 550 8 5 90 12 600 6 6 110 8 550 8 7 110 8 550 8 8 110 8 500 10 9 120 6 600 4 10 100 8 580 6 11 110 10 550 8 12 90 12 600 10

(47) The carrier obtained in above examples was used in the preparation of a catalyst through a method comprising the following.

(48) Iso-volume impregnation was employed. First, the carrier was transferred to a pear-shaped flask, and placed in a rotary evaporator, to keep the carrier in a constantly turning state. The carrier is impregnated with an aqueous solution containing a soluble cobalt salt. The pear-shaped flask was maintained to rotate for 20-40 min, and then aged overnight at room temperature. Subsequently, the product was dried for 4-12 h at 90-120? C. under normal pressure, and finally baked for 4-10 h in air at 500-600? C. and cooled to room temperature to obtain a catalyst.

(49) In actual operation, the carrier may be impregnated with the soluble cobalt salt in two times to improve the load efficiency of the carrier.

(50) In connection with the above method, the amount of the soluble cobalt salt used in the catalyst formulation in industrial production is shown in Table 3 below.

(51) TABLE-US-00003 TABLE 3 Example 1 2 3 4 5 6 7 8 9 10 11 12 Soluble Cobalt nitrate 12 36 24 45.6 19.2 36 36 48 cobalt Cobalt acetate 42 36 salt Carbonyl cobalt 20 12

(52) 40 g of the carrier prepared in above examples was weighed, and impregnated with the soluble cobalt salt through the above method. Specifically, the optimized reaction conditions are shown in Table 4 below.

(53) TABLE-US-00004 TABLE 4 Drying Drying Baking Baking temperature time temperature time Example (? C.) (h) (? C.) (h) 1 90 10 550 8 2 90 10 550 8 3 90 10 550 8 4 90 10 550 8 5 90 10 550 8 6 90 10 550 8 7 90 10 550 8 8 110 8 500 10 9 120 4 600 4 10 90 12 500 10 11 100 6 600 8 12 110 10 550 4

(54) The performance of the catalyst was evaluated in a fixed bed reactor. The catalyst was activated under conditions including a temperature of 350? C., a pressure of hydrogen of 0.1 mPa, a space velocity of hydrogen of 500 h.sup.?1, and a reduction time of 24 h. The performance of the catalyst was evaluated under conditions including a H.sub.2/CO molar ratio of 2.1, a space velocity of syngas of 2000 h.sup.?1, a space velocity of 205? C., and a reaction pressure of 3.5 mPa. The performance evaluation result of the catalyst is summarized in Table 5.

(55) TABLE-US-00005 TABLE 5 Catalyst Indicator 1 2 3 4 5 6 7 8 9 10 11 12 CO conversation rate (%) 48.1 56.4 52.3 59.0 50.1 56.5 59.9 60.7 53.1 49.2 50.5 46.2 Selectivity for CH.sub.4 (wt. %) 2.3 2.6 3.0 3.1 3.8 4.2 4.9 5.1 3.7 2.9 4.0 3.6 Selectivity for fraction distilled at 73.1 83.5 66.3 64.4 78.0 77.5 85.8 81.1 79.0 67.2 75.3 68.9 155-265? C. (wt. %) Content of iso-products in fraction 78.2 83.9 80.2 79.8 76.0 75.1 84.3 84.2 77.2 80.5 81.4 78.8 distilled at 155-265? C. (wt. %) Freezing point of fraction distilled ?42 ?49 ?44 ?43 ?39 ?38 ?52 ?51 ?42 ?43 ?38 ?41 at 155-265? C. (? C.)

(56) As shown in Table 5, in the composition of the catalyst carrier prepared in Example 7, the mesoporous zirconia, silicoaluminophosphate molecular sieve, modified SBA-16, and alumina are combined at a most preferable ratio, and when the salt of the metal cobalt is loaded in a suitable amount, the performance of the catalyst is most desirable. At a high conversion rate, the selectivity for a kerosene fraction distilled at 155-265? C. can reach 85.8%, the content of iso-products reaches 84.3% and the kerosene fraction has a freezing point of ?52? C.

(57) Unless otherwise indicated, the numerical ranges involved in the invention include the end values. While particular embodiments of the invention have been shown and described, it will be obvious to those skilled in the art that changes and modifications may be made without departing from the invention in its broader aspects, and therefore, the aim in the appended claims is to cover all such changes and modifications as fall within the true spirit and scope of the invention.