Solid acid catalyst for preparing D-galactose and preparation method thereof

Abstract

Disclosed is a solid acid catalyst for preparing D-galactose and a preparation method thereof. The method includes: S1. synthesis of a skeleton carrier: S11. preparation of a sodium aluminate solution and an organic template solution; S12. mixing the sodium aluminate solution with the organic template solution, and thoroughly shaking a resulting mixture to obtain a mixed solution; S13. adding a zirconium source to the mixed solution obtained in S12, and thoroughly mixing; S14. subjecting a reaction system obtained in S13 to a hydrothermal reaction to obtain a mixed crystal ZrO.sub.2/Al.sub.2O.sub.3; and S15. rapidly heating the mixed crystal ZrO.sub.2/Al.sub.2O.sub.3 obtained in S14 until the organic template is completely ashed, and washing a resulting product with absolute ethanol to obtain a white solid ZrO.sub.2/Al.sub.2O.sub.3; and S2. soaking the skeleton carrier obtained in S1 in concentrated sulfuric acid such that sulfonyl is loaded on the skeleton carrier to obtain the target solid acid.

Claims

1. A preparation method of a solid acid catalyst for preparing D-galactose, comprising the following steps: S1. synthesis of a skeleton carrier S11. preparation of a sodium aluminate solution and an organic template solution dissolving sodium aluminate and sodium hydroxide in water to obtain the sodium aluminate solution; and dissolving a compound as an organic template and concentrated sulfuric acid in water to obtain the organic template solution; S12. mixing the sodium aluminate solution with the organic template solution, and thoroughly shaking a resulting mixture to obtain a mixed solution, wherein the organic template is tetrapropylammonium bromide (TPAB) and a mass ratio of the sodium aluminate to the organic template is 1:9; S13. adding a zirconium source to the mixed solution obtained in S12, and thoroughly mixing, wherein a molar ratio of zirconium to aluminum is (85-115):150; S14. subjecting a reaction system obtained in S13 to a hydrothermal reaction at 105 C. to 130 C. for 10 h to obtain a mixed crystal ZrO.sub.2/Al.sub.2O.sub.3; and S15. heating the mixed crystal ZrO.sub.2/Al.sub.2O.sub.3 obtained in S14 until the organic template is completely ashed, and washing a resulting product with absolute ethanol to obtain a white solid ZrO.sub.2/Al.sub.2O.sub.3, wherein the organic template is ashed at 500 C. for 30 min; and S2. soaking the skeleton carrier obtained in S1 in concentrated sulfuric acid such that sulfonyl is loaded on the skeleton carrier to obtain the solid acid catalyst.

2. The preparation method according to claim 1, wherein in S2, the concentrated sulfuric acid has a mass fraction of 98%; and a mass of the skeleton carrier is 1 to 2 times a mass of the concentrated sulfuric acid.

3. The preparation method according to claim 1, wherein in S2, the sulfonyl loading is achieved as follows: placing the skeleton carrier in the concentrated sulfuric acid at 130 C., and stirring for 3 h.

4. The preparation method according to claim 1, wherein in S11, a mass ratio of the sodium aluminate to the sodium hydroxide is 1:7; and a mass of the water is n times a total mass of the sodium aluminate and the sodium hydroxide, wherein 9<n<15.

5. The preparation method according to claim 4, wherein in S11, a mass ratio of the organic template to the concentrated sulfuric acid is 1:8; and a mass of the water is m times a total mass of the organic template and the concentrated sulfuric acid, wherein 9<m<15.

6. The preparation method according to claim 1, wherein in S13, the zirconium source is zirconium sulfate.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a molecular vibration spectrum of ZrO.sub.2/Al.sub.2O.sub.3 prepared in Example 1 of the present disclosure.

DETAILED DESCRIPTION OF THE EMBODIMENTS

(2) The technical solutions of the present disclosure are described in further detail below with reference to specific examples.

Example 1

(3) A preparation method of a solid acid catalyst for preparing D-galactose was disclosed in this example, including the following steps:

(4) S1. Synthesis of a skeleton carrier

(5) S11. Preparation of a sodium aluminate solution and an organic template solution

(6) Sodium aluminate and sodium hydroxide were dissolved in water to obtain the sodium aluminate solution,

(7) where a mass ratio of sodium aluminate to sodium hydroxide was 1:7 and a mass of the water was 9 times a total mass of the sodium aluminate and sodium hydroxide; and

(8) a compound as an organic template and concentrated sulfuric acid were dissolved in water to obtain the organic template solution,

(9) where the organic template was TPAB, a mass ratio of the TPAB to the concentrated sulfuric acid (mass fraction: 98%) was 1:8, and a mass of the water was 9 times a total mass of the TPAB and the concentrated sulfuric acid.

(10) S12. The sodium aluminate solution and the organic template solution were mixed and thoroughly shaken to obtain a mixed solution,

(11) where a mass ratio of the sodium aluminate to the organic template was 1:9.

(12) S13. A zirconium source was added to the mixed solution obtained in S12, and a resulting mixture was thoroughly mixed, where a molar ratio of zirconium to aluminum was 85:150.

(13) S14. A reaction system obtained in S13 was subjected to a hydrothermal reaction to obtain a mixed crystal ZrO.sub.2/Al.sub.2O.sub.3,

(14) where the reaction system was placed in a polytetrafluoroethylene (PTFE) reactor and subjected to the hydrothermal reaction at 105 C. for 10 h to obtain the mixed crystal ZrO.sub.2/Al.sub.2O.sub.3.

(15) S15. The mixed crystal ZrO.sub.2/Al.sub.2O.sub.3 obtained in S.sub.14 was rapidly heated until the organic template was completely ashed, and then washed with absolute ethanol to obtain a white solid ZrO.sub.2/Al.sub.2O.sub.3,

(16) where the organic template was heated at a heating rate of 10 C./min to 500 C. and ashed at this temperature for 3 min.

(17) S2. The skeleton carrier obtained in S1 was soaked in concentrated sulfuric acid such that sulfonyl was loaded on the skeleton carrier to obtain the target solid acid,

(18) where the ZrO.sub.2/Al.sub.2O.sub.3 solid was added to the concentrated sulfuric acid (mass fraction: 98%) with a mass ratio of concentrated sulfuric acid to ZrO.sub.2/Al.sub.2O.sub.3 being 1:2, and

(19) the solid was soaked in the concentrated sulfuric acid at 120 C. for 3 h under stirring, then filtered out, and thoroughly washed with absolute ethanol to obtain the target solid acid ZrO.sub.2/Al.sub.2O.sub.3SO.sub.3.

Example 2

(20) A preparation method of a solid acid catalyst for preparing D-galactose was disclosed in this example, including the following steps:

(21) S1. Synthesis of a skeleton carrier

(22) S11. Preparation of a sodium aluminate solution and an organic template solution

(23) Sodium aluminate and sodium hydroxide were dissolved in water to obtain the sodium aluminate solution,

(24) where a mass ratio of sodium aluminate to sodium hydroxide was 1:7 and a mass of the water was 11 times a total mass of the sodium aluminate and sodium hydroxide; and

(25) a compound as an organic template and concentrated sulfuric acid were dissolved in water to obtain the organic template solution,

(26) where the organic template was TPAB, a mass ratio of the TPAB to the concentrated sulfuric acid (mass fraction: 98%) was 1:8, and a mass of the water was 11 times a total mass of the TPAB and the concentrated sulfuric acid.

(27) S12. The sodium aluminate solution and the organic template solution were mixed and thoroughly shaken to obtain a mixed solution,

(28) where a mass ratio of the sodium aluminate to the organic template was 1:9.

(29) S13. Zirconium sulfate was added to the mixed solution obtained in S12, and a resulting mixture was thoroughly mixed, where a molar ratio of zirconium to aluminum was 95:150.

(30) S14. A reaction system obtained in S13 was subjected to a hydrothermal reaction to obtain a mixed crystal ZrO.sub.2/Al.sub.2O.sub.3,

(31) where the reaction system was placed in a PTFE reactor and subjected to the hydrothermal reaction at 115 C. for 10 h to obtain the mixed crystal ZrO.sub.2/Al.sub.2O.sub.3.

(32) S15. The mixed crystal ZrO.sub.2/Al.sub.2O.sub.3 obtained in S14 was rapidly heated until the organic template was completely ashed, and then washed with absolute ethanol to obtain a white solid ZrO.sub.2/Al.sub.2O.sub.3,

(33) where the organic template was heated at a heating rate of 10 C./min to 500 C. and ashed at this temperature for 3 min.

(34) S2. The skeleton carrier obtained in S1 was soaked in concentrated sulfuric acid such that sulfonyl was loaded on the skeleton carrier to obtain the target solid acid,

(35) where the ZrO.sub.2/Al.sub.2O.sub.3 solid was added to the concentrated sulfuric acid (mass fraction: 98%) with a mass ratio of concentrated sulfuric acid to ZrO.sub.2/Al.sub.2O.sub.3 being 1:2, and

(36) the solid was soaked in the concentrated sulfuric acid at 120 C. for 3 h under stirring, then filtered out, and thoroughly washed with absolute ethanol to obtain the target solid acid ZrO.sub.2/Al.sub.2O.sub.3SO.sub.3.

Example 3

(37) A preparation method of a solid acid catalyst for preparing D-galactose was disclosed in this example, including the following steps:

(38) S1. Synthesis of a skeleton carrier

(39) S11. Preparation of a sodium aluminate solution and an organic template solution

(40) Sodium aluminate and sodium hydroxide were dissolved in water to obtain the sodium aluminate solution,

(41) where a mass ratio of sodium aluminate to sodium hydroxide was 1:7 and a mass of the water was 13 times a total mass of the sodium aluminate and sodium hydroxide; and

(42) a compound as an organic template and concentrated sulfuric acid were dissolved in water to obtain the organic template solution,

(43) where the organic template was TPAB, a mass ratio of the TPAB to the concentrated sulfuric acid (mass fraction: 98%) was 1:8, and a mass of the water was 13 times a total mass of the TPAB and the concentrated sulfuric acid.

(44) S12. The sodium aluminate solution and the organic template solution were mixed and thoroughly shaken to obtain a mixed solution,

(45) where a mass ratio of the sodium aluminate to the organic template was 1:9.

(46) S13. Zirconium sulfate was added to the mixed solution obtained in S12, and a resulting mixture was thoroughly mixed, where a molar ratio of zirconium to aluminum was 100:150.

(47) S14. A reaction system obtained in S13 was subjected to a hydrothermal reaction to obtain a mixed crystal ZrO.sub.2/Al.sub.2O.sub.3,

(48) where the reaction system was placed in a polytetrafluoroethylene (PTFE) reactor and subjected to the hydrothermal reaction at 125 C. for 10 h to obtain the mixed crystal ZrO.sub.2/Al.sub.2O.sub.3.

(49) S15. The mixed crystal ZrO.sub.2/Al.sub.2O.sub.3 obtained in S14 was rapidly heated until the organic template was completely ashed, and then washed with absolute ethanol to obtain a white solid ZrO.sub.2/Al.sub.2O.sub.3,

(50) where the organic template was heated at a heating rate of 10 C./min to 500 C. and ashed at this temperature for 3 min.

(51) S2. The skeleton carrier obtained in S1 was soaked in concentrated sulfuric acid such that sulfonyl was loaded on the skeleton carrier to obtain the target solid acid,

(52) where the ZrO.sub.2/Al.sub.2O.sub.3 solid was added to the concentrated sulfuric acid (mass fraction: 98%) with a mass ratio of concentrated sulfuric acid to ZrO.sub.2/Al.sub.2O.sub.3 being 1:2, and

(53) the solid was soaked in the concentrated sulfuric acid at 120 C. for 3 h under stirring, then filtered out, and thoroughly washed with absolute ethanol to obtain the target solid acid ZrO.sub.2/Al.sub.2O.sub.3SO.sub.3.

Example 4

(54) A preparation method of a solid acid catalyst for preparing D-galactose was disclosed in this example, including the following steps:

(55) S1. Synthesis of a skeleton carrier

(56) S11. Preparation of a sodium aluminate solution and an organic template solution

(57) Sodium aluminate and sodium hydroxide were dissolved in water to obtain the sodium aluminate solution,

(58) where a mass ratio of sodium aluminate to sodium hydroxide was 1:7 and a mass of the water was 15 times a total mass of the sodium aluminate and sodium hydroxide; and

(59) a compound as an organic template and concentrated sulfuric acid were dissolved in water to obtain the organic template solution,

(60) where the organic template was TPAB, a mass ratio of the TPAB to the concentrated sulfuric acid (mass fraction: 98%) was 1:8, and a mass of the water was 15 times a total mass of the TPAB and the concentrated sulfuric acid.

(61) S12. The sodium aluminate solution and the organic template solution were mixed and thoroughly shaken to obtain a mixed solution,

(62) where a mass ratio of the sodium aluminate to the organic template was 1:9.

(63) S13. Zirconium sulfate was added to the mixed solution obtained in S12, and a resulting mixture was thoroughly mixed, where a molar ratio of zirconium to aluminum was 115:150.

(64) S14. A reaction system obtained in S13 was subjected to a hydrothermal reaction to obtain a mixed crystal ZrO.sub.2/Al.sub.2O.sub.3,

(65) where the reaction system was placed in a polytetrafluoroethylene (PTFE) reactor and subjected to the hydrothermal reaction at 130 C. for 10 h to obtain the mixed crystal ZrO.sub.2/Al.sub.2O.sub.3.

(66) S15. The mixed crystal ZrO.sub.2/Al.sub.2O.sub.3 obtained in S14 was rapidly heated until the organic template was completely ashed, and then washed with absolute ethanol to obtain a white solid ZrO.sub.2/Al.sub.2O.sub.3,

(67) where the organic template was heated at a heating rate of 10 C./min to 500 C. and ashed at this temperature for 3 min.

(68) S2. The skeleton carrier obtained in S1 was soaked in concentrated sulfuric acid such that sulfonyl was loaded on the skeleton carrier to obtain the target solid acid,

(69) where the ZrO.sub.2/Al.sub.2O.sub.3 solid was added to the concentrated sulfuric acid (mass fraction: 98%) with a mass ratio of concentrated sulfuric acid to ZrO.sub.2/Al.sub.2O.sub.3 being 1:2, and

(70) the solid was soaked in the concentrated sulfuric acid at 120 C. for 3 h under stirring, then filtered out, and thoroughly washed with absolute ethanol to obtain the target solid acid ZrO.sub.2/Al.sub.2O.sub.3SO.sub.3.

Comparative Example 1

(71) A liquid sulfuric acid catalyst was prepared in this comparative example.

Comparative Example 2

(72) In this comparative example, a solid acid catalyst Al.sub.2O.sub.3SO.sub.3 was prepared as follows: aluminum hydroxide was soaked in H.sub.2SO.sub.4 with a mass fraction of 98% at 120 C. for 3 h under stirring, and a resulting solid was filtered out and washed with absolute ethanol to obtain the solid acid catalyst Al.sub.2O.sub.3SO.sub.3, where a mass ratio of H.sub.2SO.sub.4 to Al.sub.2O.sub.3 was 1:2.

Comparative Example 3

(73) In this comparative example, a solid acid catalyst ZrO.sub.2SO.sub.3 was prepared as follows: zirconium hydroxide was soaked in 98% H.sub.2SO.sub.4 at 120 C. for 3 h under stirring, and a resulting solid was filtered out and washed with absolute ethanol to obtain the solid acid catalyst ZrO.sub.2SO.sub.3, where a mass ratio of H.sub.2SO.sub.4 to ZrO.sub.2 was 1:2.

(74) The solid acids obtained in Examples 1 to 4 and Comparative Examples 2 and 3 each were tested for SSA with an SSA tester, and test results were shown in Table 1. The SSA of the solid acid prepared with the zirconium dioxide-modified aluminum oxide as a skeleton carrier in the present disclosure was significantly increased compared with that of the zirconium dioxide solid acid and the aluminum oxide solid acid, and the SSA of the product increased with the increase of the zirconium dioxide content. The solid acid in Example 4 had an SSA of 380 m.sup.2/g, which was 2.24 times an SSA of the pure aluminum oxide solid acid catalyst in Comparative Example 2.

(75) TABLE-US-00001 TABLE 1 SSA data of the solid acids obtained in Examples 1 to 4 and Comparative Examples 2 and 3 Group SSA (m.sup.2/g) Comparative Example 2 169 Comparative Example 3 342 Example 1 345 Example 2 367 Example 3 371 Example 4 380

(76) The catalytic efficiency of the catalyst obtained in each of Examples 1 to 4 and Comparative Examples 1 to 3 was tested, and specific test data were shown in Table 2.

(77) Lactose and a catalyst were added in a mass ratio of 1:0.1 to a reactor to allow a reaction under catalysis for 3 h, and a residual lactose content in a resulting reaction solution was tested according to the liquid chromatography (LC) method in the 2015 Chinese Pharmacopoeia:

(78) With amino-bonded silica gel as a filler, acetonitrile-water (70:30) as a mobile phase, and a column temperature of 45 C., 10 L of a solution was allowed to pass through a chromatographic column at a flow rate of 1.0 mL/min, and a lactose content was tested at a wavelength of 238 nm; and a residual lactose content in each reaction solution was tested.

(79) Catalytic efficiency=(original lactose contentresidual lactose content)/original lactose content*100%.

(80) TABLE-US-00002 TABLE 2 Catalytic efficiency of the catalysts in Examples 1 to 4 and Comparative Examples 1 to 3 Group Catalytic efficiency/% Comparative Example 1 78 Comparative Example 2 61 Comparative Example 3 55 Example 1 79 Example 2 81 Example 3 83 Example 4 86

(81) In Comparative Example 2, aluminum oxide alone is used as a carrier for a solid acid, and a limited number of acidic groups are linked due to small SSA, resulting in low catalytic efficiency of the corresponding catalyst. In Comparative Example 3, zirconium dioxide itself exhibits poor linking performance for acidic groups, resulting in undesirable catalytic efficiency.

(82) Zirconium has an atomic volume of 14.1 cm.sup.3/mol and aluminum has an atomic volume of 10.0 cm.sup.3/mol. In the present disclosure, a molar ratio of zirconium to aluminum is controlled actually to increase an SSA of a product through the combination of zirconium dioxide and aluminum oxide, increase an exposed surface of active sites of aluminum, and increase a number of acidic groups linked to aluminum. It can be known from the comparison between Comparative Examples 2 and 3 and Examples 1 to 4 that the present disclosure controls a molar ratio of zirconium to aluminum to improve the catalytic efficiency. FIG. 1 shows an infrared (IR) spectrum of a sheet sample of the ZrO.sub.2/Al.sub.2O.sub.3 prepared in Example 1 of the present disclosure in an IR spectrometer. Specific spectrum analysis is as follows: an absorption peak of hydroxyl appears at 2,900, an IR characteristic peak of zirconium dioxide (ZrOZr bond) appears at 674 cm.sup.1, and L acid characteristic peaks of aluminum oxide appear at 1,448 and 1,512. It can be known from the above results that characteristic peaks of zirconium dioxide and aluminum oxide appear during the test of the sample, indicating that ZrO.sub.2/Al.sub.2O.sub.3 is prepared in Example 1.

(83) The catalytic efficiency of the solid acid catalyst provided in the present disclosure is comparable to or even better than the catalytic efficiency of the liquid acid catalyst, indicating significant improvement of the catalytic efficiency.

(84) The recycling effects of the solid acid catalysts obtained in Examples 1 to 4 and Comparative Examples 2 and 3 each were tested, and a specific operation method was as follows:

(85) Ethanol was added to a mixed solution obtained after a catalytic reaction, a resulting mixture was stirred to precipitate unisomerized lactose and a part of the solid acid catalyst in the mixed solution, and a precipitated substance was filtered out to obtain a solution x, where a volume of the ethanol was of a volume of the mixed solution obtained after the catalytic reaction; and

(86) ethanol was added to the solution x with a volume of the ethanol being twice a volume of the solution x to obtain a pure solid acid catalyst and an isomerized lactose solution y, and the isomerized lactose solution y was subjected to distillation to remove ethanol (ethanol could be reused) to obtain a monosaccharide-containing mixed solution. In the present disclosure, unisomerized lactose in the isomerized mixed solution was selectively precipitated and the solid acid was further separated through different concentrations.

(87) A pure solid acid catalyst recovered after each catalysis of the solid acid catalyst of the present disclosure was reused five times to test a recycling effect of the solid acid catalyst, and specific test results were shown in Table 3.

(88) TABLE-US-00003 TABLE 3 Catalytic efficiency of the solid acid catalysts obtained in Examples 1 to 4 and Comparative Examples 2 and 3 during five times of catalysis First Second Third Fourth Fifth Group cycle/% cycle/% cycle/% cycle/% cycle/% Comparative 61 55 49 42 34 Example 2 Comparative 69 66 65 64 61 Example 3 Example 1 79 77 76 74 71 Example 2 81 78 77 75 74 Example 3 83 82 80 77 75 Example 4 86 84 81 78 77

(89) It can be seen from the data in Table 3 that the solid acid catalyst provided by the present disclosure can be recycled; and after zirconium dioxide is added to the carrier, the stability of the overall structure of the solid acid catalyst is increased, and when the solid acid catalyst is repeatedly used, the catalytic efficiency of the solid acid catalyst decreases slowly. Therefore, it can be concluded that, because the composite skeleton of zirconium dioxide and aluminum oxide has high stability, the solid acid catalyst can be repeatedly used many times, which is conducive to industrial production.