CN1214333A - Process of hydrogenating glucose to prepare sorbierite - Google Patents
Process of hydrogenating glucose to prepare sorbierite Download PDFInfo
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Abstract
Sorbitol preparing process includes contacting the water solution of glucose with hydrogen under conentional hydrogenation condition and in the presence of catalyst. The catalyst is one alloy catalyst comprising Ni 45-91 wt%, Fe or Mo 0.5-10 wt%, P 0.5-10 wt% and the balance Al, and it has specific surface area of 50-130 sq m/g and specific X-ray diffraction spectrum.
Description
The present invention relates to a process for the preparation of compounds having hydroxyl groups attached to carbon atoms by reduction of oxygen-containing functional groups, and more particularly to a process for the preparation of sorbitol by hydrogenation of glucose.
Sorbitol is a widely used chemical product, mainly used as raw material for synthesizing vitamin C, as raw material for producing explosive, as medicine (such as syrup), as additive for skin cream, detergent and toothpaste or as thickening agent for paper and fiber, as well as synthetic resin, surfactant and defoaming agent.
Sorbitol is generally prepared by a glucose reduction method, and sorbitol can be prepared by contacting an aqueous glucose solution with hydrogen in the presence of a catalyst under suitable process conditions according to the following formula:
meanwhile, mannitol and/or fructose can be generated as byproducts. The catalyst widely used in industry is an active nickel (e.g., Raney Ni) catalyst, but the conversion of glucose is low using this catalyst.
US4,382,150 discloses a process for preparing a corresponding polyol by hydrogenating an aqueous solution of a sugar, comprising contacting a reaction medium consisting essentially of a solution of said sugar with a catalyst under hydrogenation conditions and recovering the resulting polyol. The catalyst consists essentially of nickel dispersed on titanium oxide. Although the method is superior to the Raney Ni method, the conversion capacity of glucose and the selectivity of sorbitol are not high enough. For example, according to the description of example 3, at a reaction temperature of 120 ℃, a reaction pressure of 700Psi (about 4.8 MPa), and a sugar ratio of 2 g of catalyst/60 ml of 45 wt% aqueous glucose solution, the reaction was carried out for 5 hours with a glucose conversion of only 98 wt% and a sorbitol selectivity of only 95 wt%.
US4,380,679 discloses a process for the hydrogenation of saccharides comprising treating the saccharides with hydrogen under hydrogenation conditions and in the presence of a catalyst comprising a metal of group viii of the periodic table deposited on a support comprising a carbon-containing refractory polymer having at least repeat units comprising carbon and hydrogen atoms, and recovering the hydrogenated saccharides. By adopting the method to hydrogenate glucose, when the active components of the catalyst are noble metals such as ruthenium, platinum and the like, the conversion rate of the glucose of 99.0-99.2 wt% can be obtained at 120 ℃, but the dosage of the catalyst is larger, the reaction time is overlong, the selectivity of sorbitol is only 91.3-92.8 wt%, and the noble metal catalyst is expensive, and when the active components of the catalyst are nickel, the conversion rate of the glucose is greatly reduced to 96 wt% under the same conditions.
US4,380,680 discloses a process for the preparation of polyols by hydrogenation of saccharides, comprising contacting an aqueous solution of the saccharide with hydrogen and a catalyst under hydrogenation conditions, said catalyst consisting essentially of a catalyst selected from the group consisting of zero valent osmium, ruthenium, palladium and platinum dispersed on α -alumina, and recovering the resulting polyol.
The invention aims to overcome the defects that the glucose conversion capacity and the sorbitol selectivity are not high enough in the existing method, and provides a method for preparing sorbitol by glucose hydrogenation, which has higher glucose conversion capacity and sorbitol selectivity.
The method provided by the invention comprises the step of contacting an aqueous solution of glucose with hydrogen under the conventional hydrogenation process condition and in the presence of a catalyst, wherein the catalyst is an alloy catalyst and comprises 45-91 wt% of nickel, 0.5-10 wt% of iron or molybdenum, 0.5-10 wt% of phosphorus and the balance of aluminum, and the specific surface of the alloy catalyst is 50-130 m2In grams and has an X-ray diffraction line as shown in figure 1 at 1 or 2, measured using a CuK α target.
According to the method provided by the invention, the hydrogenation process conditions comprise a reaction temperature of 80-160 ℃ and a reaction pressure of 1-35 MPa, and the preferable hydrogenation process conditions are a reaction temperature of 100-150 ℃ and a reaction pressure of 3-12 MPa.
The method provided by the invention can be carried out in a batch kettle type reactor, a fixed bed reactor or a magnetic stabilization bed reactor, and the feeding mode can be an up-flow or down-flow mode.
When the reactor is a batch reactor, the amount of the catalyst used relative to glucose (the ratio of the catalyst to glucose) may be as low as 0.01 wt%, preferably greater than 0.05 wt%, and more preferably 0.05 to 10 wt%. When the reactor is a fixed bed or a magnetic stabilization bed, the liquid hourly space velocity of the glucose aqueous solution can be 0.1-10 hours-1Preferably the liquid hourly space velocity is 1.0 to 7.0 hours-1. The volume ratio of hydrogen to oil (volume ratio of hydrogen to aqueous glucose solution) is 5 to 300, preferably 5 to 150.
The concentration of the aqueous glucose solution generally varies from 10% by weight to its saturation concentration, more preferably from 40 to 55% by weight.
The aqueous glucose solution may be a slightly acidic or slightly alkaline solution, and the pH may vary from 4 to 9, preferably from 5 to 8.5. The pH of the aqueous glucose solution can be adjusted with an alkaline solution, such as sodium hydroxide solution, sodium carbonate solution, or aqueous ammonia solution.
The catalyst has an X-ray diffraction line measured by using a CuK α target as shown in 1 or 2 of figure 1, a diffraction peak at an angle of 2 theta of about 45 degrees in 1 or 2 of figure 1 is a broadened diffraction peak which represents a superposed peak of a microcrystalline [ Ni (111)]surface and amorphous nickel, a diffraction peak at an angle of 2 theta of about 52 degrees in 1 of figure 1 is a diffraction peak with weaker peak intensity which represents a [ Ni (110)]surface of nickel crystals, and the active component nickel in the catalyst used in the method provided by the invention also contains structurally disordered nickel besides crystalline nickel, wherein the structurally disordered nickel comprises amorphous nickel and nickel in a transition state between the crystalline state and the amorphous state as seen from 1 or 2 of figure 1.
The catalyst preferably comprises 65-91 wt% of nickel, 1-8 wt% of iron or molybdenum, 1-5 wt% of phosphorus and the balance of aluminum.
The specific surface of the catalyst is preferably 70-120 m2Per gram.
The catalyst used in the method provided by the invention can be prepared by adopting the following method:
(1) preparing Ni-P master alloy, melting a certain amount of nickel, adding the melted nickel into a certain amount of phosphorus, and automatically alloying the nickel and the phosphorus, wherein the amount of the phosphorus is 15-30 wt% of the total amount of the nickel and the phosphorus;
(2) adding a predetermined amount of iron or molybdenum and aluminum into the Ni-P master alloy, and smelting the mixture in a vacuum smelting furnace to prepare a Ni-Fe-P-Al or Ni-Mo-P-Al alloy, wherein the amount of the iron or the molybdenum is 0.5 to 15 weight percent of that of the Ni-Fe-P-Al or Ni-Mo-P-Al alloy, and the amount of the aluminum is 40 to 60 weight percent of that of the Ni-Fe-P-Al or Ni-Mo-P-Al alloy;
(3) rapidly quenching Ni-Fe-P-Al or Ni-Mo-P-Al alloy by vacuum quenching (refer to Japanese patent laid-open No. 61-212332 and figure 2 thereof) under the conditions of copper roller linear speed of 20-40 m/s, injection pressure of 0.05-0.1 MPa and injection temperature of 1200-1500 ℃;
(4) placing the product obtained in the step (3) in a ventilation environment, and pulverizing to the maximum particle size of 300-500 meshes;
(5) and (3) placing the powdered alloy obtained in the step (4) into a 10-25 wt% sodium hydroxide aqueous solution, stirring for 0.5-5 hours at 0-50 ℃, preferably stirring for 10 minutes to 1.5 hours at 0 ℃, then stirring for 0.5-4 hours at 30-50 ℃, and washing the solid product to be neutral by using deionized water to obtain the catalyst used in the method. The sodium hydroxide is preferably used in an excess of 30 wt% or more (relative to the amount of Al in the alloy).
Compared with the existing method, the method provided by the invention has higher glucose conversion capability and higher sorbitol selectivity. For example, using the process of the present invention, a 53 wt% aqueous glucose solution is hydrogenated in a batch reactor at a reaction temperature of 130 ℃, a reaction pressure of 4.8MPa, a reaction time of 70 minutes, and a sucrose ratio of 1.1 g catalyst/150 ml 53 wt% aqueous glucose solution (about 1 wt% sucrose mixture ratio), the glucose conversion is greater than 90 wt% and the sorbitol selectivity is greater than 99 wt%. Under the same conditions, when Raney Ni catalyst produced by Degussa and Raney Ni catalyst produced by ActivatedMetal of Tennessee, USA are used, the conversion rate of glucose is only 88 wt% and 82 wt% respectivelyThe selectivity for sorbitol was only 97.4 wt.% and 98 wt.%, in that order. For another example, in the method provided by the present invention,a 53 wt% glucose aqueous solution is hydrogenated in a batch tank reactor at a reaction temperature of 120 ℃, a reaction pressure of 4.8mpa, a reaction time of 200 minutes, and a molar ratio of 1.1 g catalyst to 150 ml of 53 wt% glucose aqueous solution (about 1 wt% of sugar mixture), the glucose conversion rate is 99.5 wt%, and the sorbitol selectivity is 99.2 wt%, whereas in the method disclosed in US4,380,679, the glucose conversion rate is only 99.2 wt%, and the sorbitol selectivity is only 92.8 wt% under the same reaction temperature and pressure but a longer reaction time (300 minutes) and a larger molar ratio of sugar (2 g catalyst to 60 ml of 50 wt% glucose aqueous solution, about 6.6 wt% of sugar mixture). As another example, using the process provided by the present invention, 50 is weighed in a fixed bed reactor% of glucose aqueous solution is hydrogenated at the reaction temperature of 120 ℃, the reaction pressure of 4.8MPa and the liquid hourly space velocity of 1.0 hour-1The hydrogen to glucose molar ratio of 10 (about 18.6 by volume of hydrogen-containing oil) gave a glucose conversion of 89 wt% and a sorbitol selectivity of 100 wt%, whereas the process provided in US4,380,680 gave a glucose conversion of only 57 wt% and a sorbitol selectivity of only 95 wt% under the same conditions.
The method provided by the invention can also be used for preparing corresponding polyol by hydrogenating other saccharides, as long as glucose is replaced by other saccharides, wherein the other saccharides comprise monosaccharide and disaccharide and polysaccharide which can generate monosaccharide after hydrolysis. The monosaccharide may be, for example, mannose (mannose), galactose (galctose), talose (talose), fructose (fructose), allose (allose), altrose (altrose), idose (idose), gulose (gulose), xylose (xylose) ribose (ribose), lyxose (lyxose), arabinose (arabinose), threose (threose), erythrose (erythrose). The disaccharide may be maltose (maltose), cellobiose (cellobiose), sucrose (sucrose), lactose (lactose), for example. The polysaccharide may be starch (starch), cellulose (cllulose) and its derivatives.
The following examples further illustrate the invention.
Example 1
The invention provides a method for preparing a catalyst used in the method.
(1) Putting a certain amount of phosphorus (industrial purity) in a crucible to be compacted, melting a certain amount of nickel (industrial purity), pouring the melted nickel into a dry crucible filled with the phosphorus, automatically alloying the nickel and the phosphorus, and cooling to obtain the Ni-P master alloy.
(2) Adding quantitative iron (industrial purity) or molybdenum and aluminum (industrial purity) into quantitative Ni-P master alloy, placing in a vacuum button-twisting furnace, melting, and keeping for 10 min, wherein the vacuum degree in the furnace is 10-2Torr, temperature 1200 ℃. Argon is filled to normal pressure to prepare Ni-Fe-P-Al or Ni-Mo-P-Al alloy.
(3) And rapidly quenching the Ni-Fe-P-Al or Ni-Mo-P-Al alloy by a vacuum quenching method under the conditions that the linear velocity of a copper roller is 30 m/s, the injection pressure is 0.08 MPa and the injection temperature is 1300 ℃.
(4) And (4) placing the product obtained in the step (3) in a ventilation environment to be pulverized until the maximum particle size is 300 meshes.
(5) And weighing a certain amount of the product (powdered alloy) obtained in the step (4), adding the product into a certain amount of sodium hydroxide aqueous solution, stirring for certain time at 0 ℃ and 40 ℃, and washing the solid product to be neutral by using deionized water to obtain the catalystused in the method. The amounts of phosphorus, nickel, iron or molybdenum, aluminum and the amount of Ni-P master alloy are given in Table 1, and the amounts of the product (alloy after pulverization) obtained in (4), the amount of aqueous sodium hydroxide solution, the stirring time at 0 ℃ and the stirring time at 40 ℃ are given in Table 2. Table 3 shows the composition and specific surface of the prepared catalyst, wherein catalyst A, B, C has an X-ray diffraction pattern as shown in 1 in fig. 1, and catalyst D, E, F, G, H, I has an X-ray diffraction pattern as shown in 2 in fig. 1.
The catalyst composition is measured by adopting a plasma emission spectrometry (ICP), the specific surface is measured by adopting a low-temperature nitrogen adsorption BET method, an X-ray diffraction spectrum diagram is measured on a Japan science D/max-IIA type X-ray diffractometer by using a CuK α target, Ni filtering is carried out, the power is 40 multiplied by 30VA, and the 2 theta angle is scanned between 30 and 80 degrees.
TABLE 1
| Example numbering | The dosage of each substance is gram | |||||
| Phosphorus (P) | Nickel (II) | Iron | Molybdenum (Mo) | Aluminium | Ni- | |
| 1 | 20.0 | 80.0 | 0 | 1.0 | 54.0 | 45.0 |
| 2 | 20.0 | 80.0 | 0 | 1.0 | 50.0 | 49.0 |
| 3 | 20.0 | 80.0 | 0 | 1.0 | 44.0 | 55.0 |
| 4 | 20.0 | 80.0 | 2.0 | 0 | 53.0 | 45.0 |
| 5 | 20.0 | 80.0 | 2.0 | 0 | 50.0 | 48.0 |
| 6 | 20.0 | 80.0 | 2.0 | 0 | 43.0 | 55.0 |
| 7 | 20.0 | 80.0 | 2.0 | 0 | 50.0 | 48.0 |
| 8 | 20.0 | 80.0 | 2.0 | 0 | 50.0 | 48.0 |
| 9 | 20.0 | 80.0 | 2.0 | 0 | 50.0 | 48.0 |
TABLE 2
| Example numbering | Amount of alloy after pulverization, g | Amount of NaOH solution, g | Stirring time in minutes | ||
| NaOH | Water (W) |
0 |
40 | ||
| 1 | 50.0 | 110.0 | 450.0 | 10 | 60 |
| 2 | 50.0 | 110.0 | 450.0 | 10 | 60 |
| 3 | 50.0 | 110.0 | 450.0 | 10 | 60 |
| 4 | 50.0 | 110.0 | 450.0 | 10 | 90 |
| 5 | 50.0 | 110.0 | 450.0 | 10 | 60 |
| 6 | 50.0 | 110.0 | 450.0 | 10 | 60 |
| 7 | 50.0 | 110.0 | 450.0 | 30 | 30 |
| 8 | 50.0 | 110.0 | 450.0 | 30 | 30 |
| 9 | 50.0 | 110.0 | 450.0 | 60 | 30 |
TABLE 3
| Examples of the invention Numbering | Catalyst and process for preparing same Numbering | Catalyst composition by weight percent | Specific surface area of catalyst, rice2Per gram | ||||
| Ni | Fe | Mo | P | Al | |||
| 1 | A | 70.0 | 0 | 1.5 | 1.8 | 26.7 | 74 |
| 2 | B | 83.0 | 0 | 1.5 | 1.8 | 13.7 | 98 |
| 3 | C | 90.0 | 0 | 1.5 | 1.8 | 6.7 | 115 |
| 4 | D | 70.0 | 4.9 | 0 | 2.8 | 22.3 | 92 |
| 5 | E | 75.8 | 4.9 | 0 | 2.8 | 16.5 | 96 |
| 6 | F | 80.0 | 4.9 | 0 | 2.8 | 12.3 | 100 |
| 7 | G | 77.8 | 4.9 | 0 | 2.8 | 14.5 | 97 |
| 8 | H | 74.8 | 4.9 | 0 | 2.8 | 17.5 | 95 |
| 9 | I | 75.0 | 6.0 | 0 | 3.0 | 16.0 | 96 |
Examples 10 to 25
Sorbitol is prepared according to the method provided by the invention.
Charging hydrogen to 1MPa in a batch reactor, emptying to replace the air in the reactor, continuously replacing for three times, adding 150 ml of 53 wt% glucose aqueous solution with the pH value of 8.35 in the batch reactor, respectively adding 1.1 g of catalysts A to I, charging hydrogen, stirring, heating to react for a certain time at a certain reaction temperature and reaction pressure, cooling to room temperature, analyzing the composition of the solution after the reaction by using high performance liquid chromatography, and calculating the conversion rate of glucose and the selectivity of sorbitol, wherein the reaction conditions, the use amounts of the raw materials and the reaction results are listed in tables 4 and 5. Wherein the conversion rate of glucose and the selectivity of sorbitol are calculated by the following formulas:
comparative examples 1 to 2
The preparation of sorbitol is carried out by using Raney Ni as catalyst.
Sorbitol was prepared in the same manner as in examples 10, 11, 13 to 15 and 22 to 25, except that the catalysts used were Raney Ni catalyst manufactured by Degussa, numbered J (X-ray diffraction line of J measured with CuK α target is shown in FIG. 1 as 4) and Raney Ni catalyst manufactured by Activated Metal, Tenn., USA, numbered K (X-ray diffraction line of K measured with CuK α target is shown in FIG. 1 as 3), and the reaction conditions and the reaction results are shown in tables 4 to 5.
Comparative example 3
This comparative example refers directly to the results of example 2 of US4,380,679, the reaction temperature and pressure were the same as example 18, the sugar ratio and reaction time were both greater than example 18, and the reaction conditions and results are listed in tables 4-5.
TABLE 4
| Example numbering | Catalyst numbering | Amount of catalyst used, g | Glucose solution | ||
| Concentration, weight% | Dosage in ml | pH value | |||
| 10 | A | 1.1 | 53 | 150 | 8.35 |
| 11 | B | 1.1 | 53 | 150 | 8.35 |
| 12 | B | 1.1 | 53 | 150 | 8.35 |
| 13 | C | 1.1 | 53 | 150 | 8.35 |
| 14 | D | 1.1 | 53 | 150 | 8.35 |
| 15 | E | 1.1 | 53 | 150 | 8.35 |
| 16 | E | 1.1 | 53 | 150 | 5.40 |
| 17 | E | 1.1 | 53 | 150 | 8.35 |
| 18 | E | 1.1 | 53 | 150 | 8.35 |
| 19 | E | 1.1 | 53 | 150 | 8.35 |
| 20 | E | 1.1 | 53 | 150 | 8.35 |
| 21 | E | 1.1 | 53 | 150 | 8.35 |
| 22 | F | 1.1 | 53 | 150 | 8.35 |
| 23 | G | 1.1 | 53 | 150 | 8.35 |
| 24 | H | 1.1 | 53 | 150 | 8.35 |
| 25 | I | 1.1 | 53 | 150 | 8.35 |
| Comparative example 1 | J | 1.1 | 53 | 150 | 8.35 |
| Comparative example 2 | K | 1.1 | 53 | 150 | 8.35 |
| Comparative example 3 | US4,380,679 | 2.0 | 50 | 60 | - |
TABLE 5
| Example numbering | The temperature of the reaction is controlled by the temperature, ℃ | the reaction pressure is set to be higher than the reaction pressure, megapascals | The reaction time is as long as possible, is divided into | The conversion rate of the glucose is increased, by weight percent | The selectivity of the sorbitol is high, by weight percent |
| 10 | 130 | 4.8 | 70 | 91.2 | 100 |
| 11 | 130 | 4.8 | 70 | 94.3 | 99.6 |
| 12 | 130 | 4.8 | 70 | 98.3 | 99.1 |
| 13 | 130 | 4.8 | 70 | 92.5 | 99.6 |
| 14 | 130 | 4.8 | 70 | 90.2 | 100 |
| 15 | 130 | 4.8 | 70 | 96.6 | 99.4 |
| 16 | 130 | 4.8 | 70 | 95.5 | 99.6 |
| 17 | 140 | 4.8 | 70 | 100 | 99.2 |
| 18 | 120 | 4.8 | 200 | 99.5 | 99.2 |
| 19 | 130 | 3.0 | 70 | 84.8 | 100 |
| 20 | 130 | 7.0 | 70 | 98.9 | 99.2 |
| 21 | 130 | 9.0 | 70 | 100 | 99.4 |
| 22 | 130 | 4.8 | 70 | 94.5 | 99.4 |
| 23 | 130 | 4.8 | 70 | 92.1 | 100 |
| 24 | 130 | 4.8 | 70 | 94.4 | 99.5 |
| 25 | 130 | 4.8 | 70 | 94.4 | 99.4 |
| Comparative example 1 | 130 | 4.8 | 70 | 88.0 | 97.4 |
| Comparative example 2 | 130 | 4.8 | 70 | 82.0 | 98 |
| Comparative example 3 | 120 | 4.8 | 300 | 99.2 | 92.8 |
From the results in tables 4 and 5, it can be seen that under the conditions of a reaction temperature of 130 ℃, a reaction pressure of 4.8mpa, a reaction time of 70 minutes and a sugar/catalyst ratio of 1.1 g catalyst/150 ml of 53 wt% aqueous glucose solution, the glucose conversion rate of the method provided by the present invention is higher than 90 wt%, and the sorbitol selectivity is higher than 99 wt%, whereas under the same conditions, the use of Raney Ni catalyst manufactured by Degussa corporation results in a glucose conversion rate of only 88 wt%, and a sorbitol selectivity of only 97.4 wt%. The Raney Ni catalyst produced by Activated Metal of Tennessee, USA, has glucose conversion rate of only 82 wt% and sorbitol selectivity of only 98 wt%. According to the results of example 2 of US4,380,679, the catalyst comprising nickel and platinum supported on a carbon-containing refractory polymer has a glucose conversion of 99.2 wt.% and a sorbitol selectivity of 92.8 wt.% at a reaction temperature of 120 ℃, a reaction pressure of 4.8mpa, a reaction time of 300 minutes, and a molar sugar ratio of 2 g catalyst/60 ml of 50 wt.% aqueous glucose solution, whereas the reaction time is reduced to 200 minutes at the same reaction temperature and pressure by the method of the present invention, the glucose conversion is 99.5 wt.% and the sorbitol selectivity is as high as 99.2 wt.%. This shows that the process of the present invention has higher glucose converting capacity and higher sorbitol selectivity than the prior art.
Example 26
Sorbitol is prepared according to the method provided by the invention.
The hydrogenation reaction is carried out on a continuous micro-reactor, the feeding material is glucose aqueous solution with the pH of 5.5 and the concentration of 50 weight percent, the reaction temperature is 120 ℃, the reaction pressure is 4.8MPa, and the liquid hourly space velocity is 1.0 hour-1The molar ratio of hydrogen to glucose was 10, the catalyst was E, the amount of the catalyst was 10 ml, the reaction was stabilized for 2 hours, and then the sample was taken, and the composition of the reaction product was analyzed by high performance liquid chromatography, whereby the conversion of glucose was 89% by weight and the selectivity of sorbitol was 100% by weight.
Comparative example 4
This comparative example refers directly to the results of example 3 of US4,380,680, the reaction conditions being the same as example 26, glucose conversion 57 wt% and sorbitol selectivity 95 wt%.
The results of example 26 and comparative example 4 also show that the process of the present invention provides higher glucose conversion and sorbitol selectivity than the prior art.
Example 27
Sorbitol is prepared according to the method provided by the invention.
The hydrogenation reaction is carried out in a magnetic stabilization bed reactor, the magnetic stabilization bed reactor is composed of a reaction tube and an external magnetic field, the external magnetic field is a uniform stabilization magnetic field along the axial direction of the reaction tube, the magnetic field is provided by a direct current power supply and Helmholtz (Helmholtz) coils which are uniformly distributed along the axial direction of the reaction tube, wherein the internal diameter of the Helmholtz coils is 55 mm, the external diameter of the Helmholtz coils is 165 mm, the height of the Helmholtz coils is 35 mm, the number of turns of the Helmholtz coils is 370 turns, and the reaction tube is made of a stainless steel tube which is good in permeability and. Adding 10 ml of 300-500 mesh catalyst E into a reaction tube, adjusting a direct current power supply to ensure that the magnetic field intensity reaches 400.1 oersted, pumping glucose aqueous solution with the pH value of 8.35 and the concentration of 53 weight percent, introducing hydrogen, and reacting at the temperature of 140 ℃, the reaction pressure of 7.0 MPa and the liquid hourly space velocity of 5 hours at the reaction temperature of 7.0 MPa-1Glucose was performed under the condition that the volume ratio of hydrogen to glucose solution was 100The hydrogenation reaction of (1) was carried out for 2 hours after the operation was stabilized, and the results of sampling analysis showed that the conversion of glucose was 90.2 wt% and the selectivity of sorbitol was 100 wt%.
Claims (8)
1. A method for preparing sorbitol by glucose hydrogenation comprises the step of contacting an aqueous solution of glucose with hydrogen under the condition of a conventional hydrogenation process and in the presence of a catalyst, and is characterized in that the catalyst is an alloy catalyst and comprises 45-91 wt% of nickel, 0.5-10 wt% of iron or molybdenum, 0.5-10 wt% of phosphorus and the balance of aluminum, and the specific surface area of the alloy catalyst is 50-130 m2In grams and has an X-ray diffraction line as shown in FIG. 1 at 1 or 2, measured using a CuK α target.
2. The method of claim 1, wherein the hydrogenation process conditions include a reaction temperature of 100 to 150 ℃ and a reaction pressure of 3 to 12 MPa.
3. The process according to claim 1 or 2, characterized in that the contacting of the aqueous glucose solution with hydrogen is carried out in a batch reactor, a fixed bed reactor or a magnetically stabilized bed reactor.
4. The method of claim 3, wherein the liquid hourly space velocity of the aqueous glucose solution is 1.0-7.0 hr when the reactor is a fixed bed reactor or a magnetically stabilized bed reactor-1And the volume ratio of hydrogen to oil is 5-150.
5. The method according to claim 3, wherein the ratio of sugar to the agent is 0.05 to 10% by weight when the reactor is a batch tank reactor.
6. The method according to claim 1, wherein the aqueous glucose solution has a pH of 5 to 8.5.
7. The method of claim 1, wherein the catalyst comprises 65 to 90 wt% nickel, 1 to 8 wt% iron or molybdenum, 1 to 5 wt% phosphorus, and the balance aluminum.
8. The method according to claim 1 or 7, wherein the specific surface area of the catalyst is 70 to 120 m2Per gram.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107473934A (en) * | 2017-08-29 | 2017-12-15 | 中国科学技术大学 | A kind of preparation method of sorbierite |
| CN109107581A (en) * | 2017-06-22 | 2019-01-01 | 长春美禾科技发展有限公司 | A kind of acid resisting alloy catalyst |
| CN110813297A (en) * | 2019-10-15 | 2020-02-21 | 厦门大学 | Synthesis method of sugar alcohol |
| CN110862298A (en) * | 2019-11-08 | 2020-03-06 | 黑龙江新和成生物科技有限公司 | Preparation method of sorbitol |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4380679A (en) * | 1982-04-12 | 1983-04-19 | Uop Inc. | Hydrogenation of saccharides |
| US4380680A (en) * | 1982-05-21 | 1983-04-19 | Uop Inc. | Method for hydrogenating aqueous solutions of carbohydrates |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109107581A (en) * | 2017-06-22 | 2019-01-01 | 长春美禾科技发展有限公司 | A kind of acid resisting alloy catalyst |
| CN107473934A (en) * | 2017-08-29 | 2017-12-15 | 中国科学技术大学 | A kind of preparation method of sorbierite |
| CN107473934B (en) * | 2017-08-29 | 2020-04-07 | 中国科学技术大学 | Preparation method of sorbitol |
| CN110813297A (en) * | 2019-10-15 | 2020-02-21 | 厦门大学 | Synthesis method of sugar alcohol |
| CN110813297B (en) * | 2019-10-15 | 2021-04-30 | 厦门大学 | Synthesis method of sugar alcohol |
| CN110862298A (en) * | 2019-11-08 | 2020-03-06 | 黑龙江新和成生物科技有限公司 | Preparation method of sorbitol |
| CN110862298B (en) * | 2019-11-08 | 2023-04-11 | 黑龙江新和成生物科技有限公司 | Preparation method of sorbitol |
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