CN112044433B - Catalyst for synthesizing sorbitol and preparation method and application thereof - Google Patents
Catalyst for synthesizing sorbitol and preparation method and application thereof Download PDFInfo
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- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/18—Reducing with gases containing free hydrogen
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
Abstract
The invention discloses a catalyst for synthesizing sorbitol, which comprises active carbon, ru and an auxiliary metal, wherein the Ru and the auxiliary metal are loaded on the active carbon, and the mass percentage content of the Ru in the catalyst is 3-4%, and the mass percentage content of the auxiliary metal is 1-2%; the assistant metal comprises Ce and an assistant metal A, and the assistant metal A is La, mo, ga, yb or In. In addition, the invention also provides a method for preparing the catalyst and a method for synthesizing sorbitol by catalyzing glucose hydrogenation by using the catalyst. The catalyst for synthesizing sorbitol comprises activated carbon, ru and an auxiliary metal, wherein the Ru and the auxiliary metal are loaded on the activated carbon, and when the catalyst is used for catalyzing and synthesizing sorbitol, the conversion rate of raw materials reaches 100%, the highest selectivity can reach 99.2%, the activity is high, the selectivity is good, the cost is low, and the catalyst has extremely high popularization and application values.
Description
Technical Field
The invention belongs to the technical field of noble metal catalysts, and particularly relates to a catalyst for synthesizing sorbitol as well as a preparation method and application thereof.
Background
Sorbitol is used as a bulk industrial chemical, is widely applied in the fields of food and cosmetic additives, can be used as an important intermediate for synthesizing vitamin C and the like, can be used as a precursor for producing industrial products such as isosorbide, glycol, glycerol and the like, and is screened as one of twelve bio-based platform compounds with the greatest application prospect by the U.S. department of energy. At present, the synthesis method of sorbitol mainly comprises the following steps: electrolytic processes, microbial fermentation processes and catalytic hydrogenation processes. The preparation of sorbitol by electroreduction of glucose usually faces huge power consumption, which hinders large-scale application of the electroreduction process, and fermentation of glucose using specific enzymes or microorganisms as media usually requires selection of the enzymes or microorganisms, which is expensive in cost, and the microorganisms after reaction are difficult to separate from raw materials and products, so that the enzymes and microorganisms cannot be reused. The earliest catalyst for realizing industrialization in a catalytic hydrogenation method is a Raney-Ni catalyst, and then a great deal of research and modification are carried out to improve the reaction activity and selectivity of the catalyst glucose for synthesizing sorbitol, however, the reaction system using the Raney-Ni catalyst still has the problems of harsh reaction conditions, poor recycling and the like.
In recent years, researchers aim at carrier catalysts or homogeneous catalysts, and find that supported metal catalysts and homogeneous catalysts show higher activity and stability in the process of glucose hydrogenation reaction. The Chinese patent application with publication number of 201811216116.3, 3.1.2019 discloses a molecular sieve supported nickel catalyst and the catalyst is used for preparing sorbitol by catalytic hydrogenation of glucose, the conversion rate can reach 100%, but the selectivity is only 93.3%. The Chinese patent application document with the publication date of 12 and 15 in 2017 and the application number of 201710757968.2 discloses a method for hydrogenating glucose by using a half sandwich type iridium complex as a catalyst, wherein the yield can reach 95.6% at most, but the problem that the product and the catalyst are not separated well exists. Research and development of a catalyst with high performance of catalyzing the conversion of glucose into sorbitol for wide popularization and application is an effective means for solving the problems.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a catalyst for synthesizing sorbitol, a preparation method and an application thereof, aiming at the defects of the prior art. The catalyst for synthesizing sorbitol comprises activated carbon, ru and an auxiliary metal, wherein the Ru and the auxiliary metal are loaded on the activated carbon, and when the catalyst is used for catalyzing and synthesizing sorbitol, the conversion rate of raw materials reaches 100%, the highest selectivity can reach 99.2%, the activity is high, the selectivity is good, the cost is low, and the catalyst has extremely high popularization and application values.
In order to solve the technical problems, the invention adopts the technical scheme that: the catalyst for synthesizing the sorbitol is characterized by comprising active carbon, ru and an auxiliary metal, wherein the Ru and the auxiliary metal are loaded on the active carbon, and the mass percentage content of the Ru in the catalyst is 3-4% and the mass percentage content of the auxiliary metal is 1-2%;
the assistant metal comprises Ce and an assistant metal A, and the assistant metal A is La, mo, ga, yb or In.
Further, the catalyst for synthesizing sorbitol is characterized by comprising active carbon, ru and an auxiliary metal, wherein the Ru and the auxiliary metal are loaded on the active carbon, and the mass percentage of the Ru in the catalyst is 3% -4%, and the mass percentage of the auxiliary metal is 1% -2%;
the auxiliary metal is Ce and auxiliary metal A, and the auxiliary metal A is La, mo, ga, yb or In.
The catalyst for synthesizing the sorbitol is characterized in that the mass of Ce is 0.5-4 times of that of the auxiliary agent metal A; the specific surface area of the activated carbon is 1800m 2 /g～2000m 2 /g。
The catalyst for synthesizing sorbitol is characterized in that the mass percent of Ru in the catalyst is 4%, the mass percent of the auxiliary metal is 1%, the mass percent of the auxiliary metal is Ce and Mo, and the mass percent of Ce and Mo is 0.5%.
In addition, the invention also provides a method for preparing the catalyst for synthesizing the sorbitol, which is characterized by comprising the following steps:
step one, mixing an aqueous solution containing an auxiliary agent metal soluble salt and sodium dodecyl sulfate with activated carbon, and stirring for 45-90 min to obtain a mixed system;
step two, dropwise adding an aqueous solution of a reducing agent into the mixed system obtained in the step one, and stirring for 12-24 hours after dropwise adding is finished to obtain activated carbon slurry containing an auxiliary metal;
and step three, dropwise adding a ruthenium trichloride hydrochloric acid solution into the activated carbon slurry containing the auxiliary metal in the step two, stirring for 8-10 h after dropwise adding, drying, and reducing for 3-5 h by hydrogen to obtain the catalyst for synthesizing the sorbitol.
The method is characterized in that the specific surface area of the activated carbon after pretreatment in the step one is 1800m 2 /g～2000m 2 Activated carbon per gram, the method of pretreatment comprising:
step 101, setting the specific surface area to 600m 2 /g～650m 2 Mixing the activated carbon per gram with a sodium bicarbonate aqueous solution, stirring for 20-30 h, and drying to obtain dried activated carbon;
step 102, in a nitrogen atmosphere, carrying out heat treatment on the dried activated carbon obtained in the step 101 in a tube furnace to obtain heat-treated activated carbon; the heat treatment is two-stage heat treatment, the temperature of the first stage heat treatment is 250-320 ℃, the heat preservation time is 1-2 h, the temperature of the second stage heat treatment is 760-850 ℃, and the heat preservation time is 2-3 h;
and 103, washing the activated carbon subjected to the heat treatment in the step 102 to be neutral, and drying to obtain the pretreated activated carbon.
The method is characterized in that in the step 101, the mass percentage of the sodium bicarbonate aqueous solution is 5-20%; in step 102, the temperature rising rate from the room temperature to the first stage heat treatment temperature and the temperature rising rate from the first stage heat treatment temperature to the second stage heat treatment temperature are both 5 ℃/min.
The method is characterized in that in the aqueous solution containing the assistant metal soluble salt and the sodium dodecyl sulfate in the step one, the mass of the sodium dodecyl sulfate is 5-10% of that of the assistant metal; the mass of the reducing agent in the second step is 4-8 times of that of the auxiliary metal in the first step, and the reducing agent is sodium borohydride, potassium borohydride or hydrazine hydrate; the dropping time of the aqueous solution of the reducing agent in the step two is 10-15 min; in the third step, the dripping time of the ruthenium trichloride hydrochloric acid solution is 30-60 min; in the third step, the hydrogen reduction is carried out in a tubular furnace, and the temperature of the hydrogen reduction is 400-600 ℃.
The method is characterized in that the stirring time in the step one is 60min; stirring for 24 hours in the step 101; the temperature of the first stage heat treatment in step 102 is 300 ℃ and the temperature of the second stage heat treatment is 800 ℃.
On the other hand, the invention also provides a method for synthesizing sorbitol by catalyzing glucose hydrogenation by using the catalyst, which is characterized by comprising the following steps: reacting glucose aqueous solution with a catalyst in a hydrogen atmosphere of 3MPa to 4MPa, wherein the reaction temperature is 110 ℃ to 130 ℃, and the reaction time is 70min to 90min; the mass percentage content of the glucose aqueous solution is 15-30%, and the mass of the catalyst is 1-2% of the mass of glucose.
Compared with the prior art, the invention has the following advantages:
1. the catalyst for synthesizing sorbitol comprises activated carbon, ru and an auxiliary metal, wherein the Ru and the auxiliary metal are loaded on the activated carbon, when the catalyst is used for catalyzing and synthesizing sorbitol, the conversion rate of raw materials reaches 100%, the highest selectivity can reach 99.2%, the activity is high, the selectivity is good, the cost is low, and the catalyst has extremely high popularization and application values.
2. The catalyst for synthesizing the sorbitol is acidic, has more stable catalytic effect in the reaction of catalyzing and synthesizing the sorbitol, can save the step of adjusting the pH of reaction liquid, can be separated from a product system through filtration, and has simple and convenient process.
3. The method for preparing the catalyst for synthesizing the sorbitol takes the pretreated active carbon as a carrier, is stirred by a water solution containing auxiliary metal soluble salt and sodium dodecyl sulfate, is soaked in a ruthenium trichloride hydrochloric acid solution, and is reduced by high-temperature hydrogen to prepare the catalyst for synthesizing the sorbitol, wherein the metal components have higher dispersity and more uniform dispersion on the active carbon, the synergistic effect of the auxiliary metal and the active components is enhanced, and the catalytic performance of the catalyst is higher.
4. The method uses sodium bicarbonate and two-stage heat treatment to carry out pretreatment on the activated carbon, preferably the two-stage heat treatment temperature is respectively 300 ℃ and 800 ℃, the sodium bicarbonate adsorbed by the activated carbon after stirring treatment is thermally decomposed to generate carbon dioxide and water vapor to carry out erosion modification on the activated carbon and excite surface alkaline groups, the bonding strength of the surface of the activated carbon carrier and metal components is improved, and the catalytic effect of the catalyst is improved.
5. The method for preparing the catalyst for synthesizing the sorbitol has low cost, simple preparation method and easy operation and mass production.
The technical solution of the present invention is further described in detail with reference to the following examples.
Detailed Description
Example 1
The catalyst for synthesizing sorbitol comprises active carbon, ru and an auxiliary metal, wherein the Ru and the auxiliary metal are loaded on the active carbon, and the mass percentage of the Ru in the catalyst is 3% and the mass percentage of the auxiliary metal is 2%;
the additive metal is Ce and additive metal A, the additive metal A is La, and the mass percentage of Ce and La is 1%.
The preparation method of the catalyst for synthesizing sorbitol comprises the following steps:
step one, setting the specific surface area of 30g to 600m 2 Mixing the activated carbon per gram with 300mL of a 5% sodium bicarbonate aqueous solution by mass, stirring for 24 hours at normal temperature, and drying until the water content is lower than 1wt% to obtain dried activated carbon; the normal temperature is 20-25 ℃;
step two, in a nitrogen atmosphere, carrying out two-stage heat treatment on the dried activated carbon obtained in the step one in a tubular furnace to obtain heat-treated activated carbon, which specifically comprises the following steps: putting the dried activated carbon in the first step into a tubular furnace, introducing nitrogen into the tubular furnace, raising the temperature of the tubular furnace from room temperature to 300 ℃, preserving the heat for 1h, then raising the temperature of the tubular furnace from 300 ℃ to 800 ℃, preserving the heat for 2h, wherein as a preferred embodiment, the temperature raising rate from room temperature to 300 ℃ is 2 ℃/min, the temperature raising rate from 300 ℃ to 800 ℃ is 10 ℃/min, and the room temperature is 20-25 ℃;
step three, washing the activated carbon subjected to the heat treatment in the step two to be neutral, and drying until the water content is lower than 1wt% in mass percentage to obtain pretreated activated carbon; the specific surface area of the pretreated activated carbon is 1800m 2 /g；
Step four, mixing 0.3098g Ce (NO) 3 ) 3 .6H 2 O、0.3118g La(NO 3 ) 3 .6H 2 Dissolving O and 0.01g of sodium dodecyl sulfate in water, diluting to 150mL, uniformly stirring to obtain an aqueous solution containing an auxiliary agent metal soluble salt and sodium dodecyl sulfate, pouring the 150mL of aqueous solution containing the auxiliary agent metal soluble salt and the sodium dodecyl sulfate into a container filled with 9.5g of the pretreated activated carbon obtained in the third step under the condition of stirring, and continuously stirring for 60min to obtain a mixed system;
step five, dripping 100mL of aqueous solution of a reducing agent with the concentration of 8g/L into the mixed system obtained in the step four, and stirring for 12 hours after finishing dripping to obtain activated carbon slurry containing the auxiliary agent metal; the reducing agent is sodium borohydride, and the time for dripping the aqueous solution of the reducing agent is 10min;
step six, dissolving 0.8g of ruthenium trichloride trihydrate with dilute hydrochloric acid and diluting to 150mL to obtain a ruthenium trichloride hydrochloric acid solution, dropwise adding the 150mL of ruthenium trichloride hydrochloric acid solution into the activated carbon slurry containing the aid metal in the step five, stirring for 8 hours after dropwise adding, drying until the water content is lower than 1wt%, putting the dried material into a tubular furnace with hydrogen as an atmosphere, raising the temperature to 400 ℃ at the heating rate of 2 ℃/min, and preserving the heat for 5 hours to reduce the material to obtain the catalyst for synthesizing the sorbitol; the time for dripping the ruthenium trichloride hydrochloric acid solution is 30min; the dilute hydrochloric acid may be 20% by weight, and the concentration of the dilute hydrochloric acid is not limited in this embodiment.
Comparative example 1
This comparative example is the same as example 1 except that, without going through the steps one to three, the specific surface area was 600m 2 The catalyst is prepared from the activated carbon per gram through the fourth step to the sixth step.
Comparative example 2
This comparative example is the same as example 1 except that, without going through the steps one to three, the specific surface area was 1800m 2 The catalyst is prepared from the activated carbon per gram through the fourth step to the sixth step.
Comparative example 3
This comparative example is the same as example 1 except that sodium lauryl sulfate was not included in step three.
Comparative example 4
This comparative example is the same as example 1 except that the first stage heat treatment temperature in step two was 200 ℃ and the second stage heat treatment temperature was 700 ℃.
Comparative example 5
This comparative example is the same as example 1 except that the first stage heat treatment temperature in step two was 350 ℃ and the second stage heat treatment temperature was 900 ℃.
Comparative example 6
This comparative example is the same as example 1 except that the catalyst was prepared without the promoter metal, i.e., without going through step four and step five.
Example 2
The catalyst for synthesizing sorbitol comprises active carbon, ru and an auxiliary metal, wherein the Ru and the auxiliary metal are loaded on the active carbon, and the mass percentage content of the Ru in the catalyst is 3.5% and the mass percentage content of the auxiliary metal is 1.5%;
the auxiliary metal is Ce and auxiliary metal A, the auxiliary metal A is Ga, the mass percent of Ce is 0.5%, and the mass percent of Ga is 1.0%.
The preparation method of the catalyst for synthesizing sorbitol comprises the following steps:
step one, setting the specific surface area of 30g to 650m 2 Mixing the activated carbon per gram with 300mL of a sodium bicarbonate aqueous solution with the mass percentage content of 10%, stirring for 24 hours at normal temperature, and drying until the water content is lower than 1wt% to obtain dried activated carbon;
step two, in a nitrogen atmosphere, carrying out two-stage heat treatment on the dried activated carbon obtained in the step one in a tubular furnace to obtain heat-treated activated carbon, which specifically comprises the following steps: putting the dried activated carbon in the step one into a tubular furnace, introducing nitrogen into the tubular furnace, heating the tubular furnace from room temperature to 300 ℃, preserving heat for 1.5h, then heating from 300 ℃ to 800 ℃, and preserving heat for 2h; as a preferred embodiment, the temperature rising rate from room temperature to 300 ℃ is 2 ℃/min, and the temperature rising rate from 300 ℃ to 800 ℃ is 10 ℃/min;
step three, washing the activated carbon subjected to the heat treatment in the step two to be neutral, and drying until the water content is lower than 1wt% in mass percentage to obtain pretreated activated carbon; the specific surface area of the pretreated activated carbon is 1890m 2 /g；
Step four, mixing 0.1549g Ce (NO) 3 ) 3 .6H 2 O、0.2525g GaCl 3 And 0.015g of sodium dodecyl sulfate is dissolved and diluted to 150mL by water, the mixture is stirred uniformly to obtain an aqueous solution containing the assistant metal soluble salt and the sodium dodecyl sulfate, under the stirring condition, the 150mL of aqueous solution containing the assistant metal soluble salt and the sodium dodecyl sulfate is poured into a container filled with 9.5g of the pretreated activated carbon obtained in the third step, and the stirring is continued for 60min to obtain a mixed system;
step five, dripping 100mL of aqueous solution of a reducing agent with the concentration of 9g/L into the mixed system obtained in the step four, and stirring for 15h after finishing dripping to obtain activated carbon slurry containing the auxiliary agent metal; the reducing agent is hydrazine hydrate, and the time for dripping the aqueous solution of the reducing agent is 10min;
step six, dissolving 0.933g of ruthenium trichloride trihydrate with dilute hydrochloric acid and diluting to 150mL to obtain a ruthenium trichloride hydrochloric acid solution, dropwise adding the 150mL of ruthenium trichloride hydrochloric acid solution into the activated carbon slurry containing the aid metal in the step five, stirring for 9 hours after dropwise adding, drying until the water content is lower than 1wt%, putting the dried material into a tubular furnace with hydrogen as an atmosphere, raising the temperature to 500 ℃ at the rate of 2 ℃/min, and preserving the temperature for 4.5 hours to reduce the material to obtain a catalyst for synthesizing sorbitol; the time for dripping the ruthenium trichloride hydrochloric acid solution is 45min; the dilute hydrochloric acid may be 20% by weight, and the concentration of the dilute hydrochloric acid is not limited in this embodiment.
Example 3
The catalyst for synthesizing the sorbitol comprises active carbon, ru and an auxiliary metal, wherein the Ru and the auxiliary metal are loaded on the active carbon, and the mass percentage of the Ru in the catalyst is 4% and the mass percentage of the auxiliary metal is 1%;
the auxiliary metal is Ce and auxiliary metal A, the auxiliary metal A is Mo, and the mass percentage of Ce and Mo is 0.5%.
The preparation method of the catalyst for synthesizing sorbitol comprises the following steps:
step one, 30g of the powder with the specific surface area of 625m 2 Mixing activated carbon per gram with 300mL of a sodium bicarbonate aqueous solution with the mass percentage of 20%, stirring for 24 hours at normal temperature, and drying until the water content is lower than 1wt% to obtain dried activated carbon;
step two, in a nitrogen atmosphere, carrying out two-stage heat treatment on the dried activated carbon obtained in the step one in a tubular furnace to obtain heat-treated activated carbon, which specifically comprises the following steps: putting the dried activated carbon in the step one into a tubular furnace, introducing nitrogen into the tubular furnace, heating the tubular furnace from room temperature to 300 ℃, preserving heat for 2 hours, then heating from 300 ℃ to 800 ℃, and preserving heat for 3 hours; as a preferred embodiment, the temperature rising rate from room temperature to 300 ℃ is 2 ℃/min, and the temperature rising rate from 300 ℃ to 800 ℃ is 10 ℃/min;
step three, washing the activated carbon subjected to the heat treatment in the step two to be neutral, and drying until the water content is lower than 1wt% in mass percentage to obtain pretreated activated carbon; the specific surface area of the pretreated activated carbon is 2000m 2 /g；
Step (ii) of4. 0.1549g Ce (NO) 3 ) 3 .6H 2 O、0.1021g(NH 4 ) 2 MoO 4 And 0.01g of sodium dodecyl sulfate is dissolved in water and diluted to 150mL, the mixture is stirred uniformly to obtain an aqueous solution containing the auxiliary agent metal soluble salt and the sodium dodecyl sulfate, under the stirring condition, the 150mL of aqueous solution containing the auxiliary agent metal soluble salt and the sodium dodecyl sulfate is poured into a container filled with 9.5g of the pretreated activated carbon obtained in the third step, and the stirring is continued for 60min to obtain a mixed system;
step five, dripping 100mL of aqueous solution of a reducing agent with the concentration of 8g/L into the mixed system obtained in the step four, and stirring for 24 hours after finishing dripping to obtain activated carbon slurry containing the auxiliary agent metal; the reducing agent is potassium borohydride, and the time for dripping the aqueous solution of the reducing agent is 15min;
step six, dissolving 1.0667g of ruthenium trichloride trihydrate with dilute hydrochloric acid and diluting to 150mL to obtain a ruthenium trichloride hydrochloric acid solution, dropwise adding the 150mL of ruthenium trichloride hydrochloric acid solution into the activated carbon slurry containing the aid metal in the step five, stirring for 10 hours after dropwise adding, drying until the water content is lower than 1wt%, putting the dried material into a tubular furnace with hydrogen as an atmosphere, raising the temperature to 600 ℃ at a heating rate of 2 ℃/min, and reducing the material by keeping the temperature for 3 hours to obtain a catalyst for synthesizing sorbitol; dripping ruthenium trichloride hydrochloric acid solution for 50min; the dilute hydrochloric acid may be 20% by weight, and the concentration of the dilute hydrochloric acid is not limited in this embodiment.
Example 4
The catalyst for synthesizing sorbitol comprises activated carbon, ru and an auxiliary metal, wherein the Ru and the auxiliary metal are loaded on the activated carbon, and the mass percentage of the Ru in the catalyst is 4% and the mass percentage of the auxiliary metal is 1%;
the auxiliary metal comprises Ce and an auxiliary metal A, the auxiliary metal A is Yb, the mass percent of Ce is 0.8%, and the mass percent of Yb is 0.2%.
The preparation method of the catalyst for synthesizing sorbitol comprises the following steps:
step one, step 30g of specific surface area 650m 2 Mixing activated carbon per gram with 300mL of a sodium bicarbonate aqueous solution with the mass percentage content of 15%, stirring for 24 hours at normal temperature, and drying until the water content is lower than 1wt% to obtain dried activated carbon;
step two, in a nitrogen atmosphere, carrying out two-stage heat treatment on the dried activated carbon obtained in the step one in a tubular furnace to obtain heat-treated activated carbon, which specifically comprises the following steps: putting the dried activated carbon in the step one into a tubular furnace, introducing nitrogen into the tubular furnace, raising the temperature of the tubular furnace from room temperature to 300 ℃, preserving the heat for 1.5h, then raising the temperature of the tubular furnace from 300 ℃ to 800 ℃, preserving the heat for 2.5h, wherein as a preferred embodiment, the temperature raising rate from room temperature to 300 ℃ is 2 ℃/min, and the temperature raising rate from 300 ℃ to 800 ℃ is 10 ℃/min;
step three, washing the activated carbon subjected to the heat treatment in the step two to be neutral, and drying until the water content is lower than 1wt% in mass percentage to obtain pretreated activated carbon; the specific surface area of the pretreated active carbon is 1900m 2 /g；
Step four, 0.2127g CeCl is added 3 .6H 2 O、0.0323g YbCl 3 And 0.01g of sodium dodecyl sulfate is dissolved by water and diluted to 150mL to obtain an aqueous solution containing the auxiliary agent metal soluble salt and the sodium dodecyl sulfate, under the condition of stirring, the 150mL of aqueous solution containing the auxiliary agent metal soluble salt and the sodium dodecyl sulfate is poured into a container filled with 9.5g of the pretreated activated carbon obtained in the third step, and the stirring is continued for 60min to obtain a mixed system;
step five, dripping 100mL of aqueous solution of a reducing agent with the concentration of 5g/L into the mixed system obtained in the step four, and stirring for 12 hours after finishing dripping to obtain activated carbon slurry containing the auxiliary agent metal; the reducing agent is hydrazine hydrate, and the time for dripping the aqueous solution of the reducing agent is 10min;
step six, dissolving 1.0667g of ruthenium trichloride trihydrate with dilute hydrochloric acid and diluting to 150mL to obtain a ruthenium trichloride hydrochloric acid solution, dropwise adding the 150mL of ruthenium trichloride hydrochloric acid solution into the activated carbon slurry containing the aid metal in the step five, stirring for 9 hours after dropwise adding, drying until the water content is lower than 1wt%, putting the dried material into a tubular furnace with hydrogen as an atmosphere, raising the temperature to 550 ℃ at a heating rate of 2 ℃/min, and reducing the material by keeping the temperature for 3.5 hours to obtain a catalyst for synthesizing sorbitol; the time for dripping the ruthenium trichloride hydrochloric acid solution is 60min; the dilute hydrochloric acid may be 20% by weight, and the concentration of the dilute hydrochloric acid is not limited in this embodiment.
Example 5
The catalyst for synthesizing the sorbitol comprises active carbon, ru and an auxiliary metal, wherein the Ru and the auxiliary metal are loaded on the active carbon, and the mass percentage of the Ru in the catalyst is 3%, and the mass percentage of the auxiliary metal is 2%;
the auxiliary metal is Ce and auxiliary metal A, the auxiliary metal A is In, the mass percent of Ce is 1.6%, and the mass percent of In is 0.4%.
The preparation method of the catalyst for synthesizing sorbitol comprises the following steps:
step one, setting the specific surface area of 30g to be 645m 2 Mixing activated carbon/g with 300mL of sodium bicarbonate aqueous solution with the mass percentage content of 8%, stirring for 24 hours at normal temperature, and drying until the water content is lower than 1wt% to obtain dried activated carbon;
step two, in a nitrogen atmosphere, carrying out two-stage heat treatment on the dried activated carbon obtained in the step one in a tubular furnace to obtain heat-treated activated carbon, which specifically comprises the following steps: placing the dried activated carbon in the step one in a tubular furnace, introducing nitrogen into the tubular furnace, raising the temperature of the tubular furnace from room temperature to 300 ℃, preserving the heat for 1h, then raising the temperature of the tubular furnace from 300 ℃ to 800 ℃, preserving the heat for 3h, wherein as a preferred embodiment, the temperature raising rate from room temperature to 300 ℃ is 2 ℃/min, and the temperature raising rate from 300 ℃ to 800 ℃ is 10 ℃/min;
step three, washing the activated carbon subjected to the heat treatment in the step two to be neutral, and drying until the water content is lower than 1wt% in mass percentage to obtain pretreated activated carbon; the specific surface area of the pretreated activated carbon is 1860m 2 /g；
Step four, mixing 0.4957gCe (NO) 3 ) 2 .6H 2 O、0.0771g InCl 3 And 0.013g of sodium dodecyl sulfate is dissolved by water and diluted to 150mL to obtain an aqueous solution containing the auxiliary agent metal soluble salt and the sodium dodecyl sulfate, under the condition of stirring, the 150mL of aqueous solution containing the auxiliary agent metal soluble salt and the sodium dodecyl sulfate is poured into a container filled with 9.5g of the pretreated activated carbon obtained in the third step, and the stirring is continued for 60min to obtain a mixed system;
step five, dripping 100mL of aqueous solution of a reducing agent with the reducing agent concentration of 14g/L into the mixed system obtained in the step four, and stirring for 18h after finishing dripping to obtain activated carbon slurry containing the auxiliary agent metal; the reducing agent is potassium borohydride, and the time for dripping the aqueous solution of the reducing agent is 12min;
step six, dissolving 0.8g of ruthenium trichloride trihydrate with dilute hydrochloric acid and diluting to 150mL to obtain a ruthenium trichloride hydrochloric acid solution, dropwise adding the 150mL of ruthenium trichloride hydrochloric acid solution into the activated carbon slurry containing the aid metal in the step five, stirring for 9 hours after dropwise adding, drying until the water content is lower than 1wt%, putting the dried material into a tubular furnace with hydrogen as an atmosphere, raising the temperature to 500 ℃ at the heating rate of 2 ℃/min, and preserving the heat for 4 hours to reduce the material to obtain the catalyst for synthesizing the sorbitol; dripping ruthenium trichloride hydrochloric acid solution for 50min; the dilute hydrochloric acid may be 20% by weight, and the concentration of the dilute hydrochloric acid is not limited in this embodiment.
Example 6
The catalyst for synthesizing sorbitol comprises active carbon, ru and an auxiliary metal, wherein the Ru and the auxiliary metal are loaded on the active carbon, and the mass percentage of the Ru in the catalyst is 3% and the mass percentage of the auxiliary metal is 2%;
the auxiliary metal is Ce and auxiliary metal A, the auxiliary metal A is La, and the mass percentage of Ce and La is 1%.
The preparation method of the catalyst for synthesizing sorbitol comprises the following steps:
step one, setting the specific surface area of 30g to be 620m 2 Mixing activated carbon per gram with 300mL of sodium bicarbonate water solution with the mass percentage of 5 percent, and stirring the mixture at normal temperatureDrying for 20 hours until the water content is lower than 1wt%, and obtaining dried active carbon;
step two, in a nitrogen atmosphere, carrying out two-stage heat treatment on the dried activated carbon obtained in the step one in a tubular furnace to obtain heat-treated activated carbon, which specifically comprises the following steps: putting the dried activated carbon in the step one into a tubular furnace, introducing nitrogen into the tubular furnace, raising the temperature of the tubular furnace from room temperature to 250 ℃, preserving the heat for 1h, then raising the temperature of the tubular furnace from 250 ℃ to 850 ℃, preserving the heat for 2h, wherein as a preferred embodiment, the temperature raising rate from room temperature to 250 ℃ is 2 ℃/min, and the temperature raising rate from 250 ℃ to 850 ℃ is 10 ℃/min;
step three, washing the activated carbon subjected to the heat treatment in the step two to be neutral, and drying until the water content is lower than 1wt% in mass percentage to obtain pretreated activated carbon; the specific surface area of the pretreated active carbon is 1800m 2 /g；
Step four, mixing 0.3098g Ce (NO) 3 ) 3 .6H 2 O、0.3118g La(NO 3 ) 3 .6H 2 Dissolving O and 0.01g of lauryl sodium sulfate in water, diluting to 150mL, uniformly stirring to obtain an aqueous solution containing the auxiliary agent metal soluble salt and the lauryl sodium sulfate, pouring the 150mL of aqueous solution containing the auxiliary agent metal soluble salt and the lauryl sodium sulfate into a container filled with 9.5g of the pretreated activated carbon obtained in the third step under the stirring condition, and continuously stirring for 45min to obtain a mixed system;
step five, dripping 100mL of aqueous solution of a reducing agent with the concentration of 8g/L into the mixed system obtained in the step four, and stirring for 12 hours after finishing dripping to obtain activated carbon slurry containing the assistant metal; the reducing agent is sodium borohydride, and the time for dripping the aqueous solution of the reducing agent is 10min;
step six, dissolving 0.8g of ruthenium trichloride trihydrate with dilute hydrochloric acid and diluting to 150mL to obtain a ruthenium trichloride hydrochloric acid solution, dropwise adding the 150mL of ruthenium trichloride hydrochloric acid solution into the activated carbon slurry containing the aid metal in the step five, stirring for 8 hours after dropwise adding, drying until the water content is lower than 1wt%, putting the dried material into a tubular furnace with hydrogen as an atmosphere, raising the temperature to 400 ℃ at the heating rate of 2 ℃/min, and preserving the heat for 4.5 hours to reduce the material to obtain a catalyst for synthesizing sorbitol; dripping ruthenium trichloride hydrochloric acid solution for 30min; the diluted hydrochloric acid may be 20% by mass, and the concentration of the diluted hydrochloric acid is not limited in this embodiment.
Example 7
The catalyst for synthesizing sorbitol comprises active carbon, ru and an auxiliary metal, wherein the Ru and the auxiliary metal are loaded on the active carbon, and the mass percentage of the Ru in the catalyst is 3% and the mass percentage of the auxiliary metal is 2%;
the auxiliary metal is Ce and auxiliary metal A, the auxiliary metal A is La, and the mass percentage of Ce and La is 1%.
The preparation method of the catalyst for synthesizing sorbitol comprises the following steps:
step one, setting the specific surface area of 30g to 630m 2 Mixing the activated carbon per gram with 300mL of a 5% sodium bicarbonate aqueous solution by mass, stirring for 30 hours at normal temperature, and drying until the water content is lower than 1wt% by mass to obtain dried activated carbon;
step two, in a nitrogen atmosphere, carrying out two-stage heat treatment on the dried activated carbon obtained in the step one in a tubular furnace to obtain heat-treated activated carbon, which specifically comprises the following steps: putting the dried activated carbon in the step one into a tubular furnace, introducing nitrogen into the tubular furnace, raising the temperature of the tubular furnace from room temperature to 320 ℃, preserving the heat for 1h, then raising the temperature to 760 ℃, and preserving the heat for 2h, wherein as a preferred embodiment, the temperature rise rate from room temperature to 320 ℃ is 2 ℃/min, and the temperature rise rate from 320 ℃ to 760 ℃ is 10 ℃/min;
step three, washing the activated carbon subjected to the heat treatment in the step two to be neutral, and drying until the water content is lower than 1wt% in mass percentage to obtain pretreated activated carbon; the specific surface area of the pretreated activated carbon is 1800m 2 /g；
Step four, mixing 0.3098g Ce (NO) 3 ) 3 .6H 2 O、0.3118g La(NO 3 ) 3 .6H 2 O and 0.01g of sodium dodecyl sulfate are dissolved in water and diluted to 150mL, and the mixture is stirred uniformlyUniformly mixing to obtain an aqueous solution containing the aid metal soluble salt and the sodium dodecyl sulfate, pouring 150mL of the aqueous solution containing the aid metal soluble salt and the sodium dodecyl sulfate into a container filled with 9.5g of the pretreated activated carbon obtained in the third step under the stirring condition, and continuously stirring for 90min to obtain a mixed system;
step five, dripping 100mL of aqueous solution of a reducing agent with the concentration of 8g/L into the mixed system obtained in the step four, and stirring for 12 hours after finishing dripping to obtain activated carbon slurry containing the auxiliary agent metal; the reducing agent is sodium borohydride, and the time for dripping the aqueous solution of the reducing agent is 10min;
step six, dissolving 0.8g of ruthenium trichloride trihydrate with dilute hydrochloric acid and diluting to 150mL to obtain a ruthenium trichloride hydrochloric acid solution, dropwise adding the 150mL of ruthenium trichloride hydrochloric acid solution into the activated carbon slurry containing the aid metal in the step five, stirring for 8 hours after dropwise adding, drying until the water content is lower than 1wt%, putting the dried material into a tubular furnace with hydrogen as an atmosphere, raising the temperature to 400 ℃ at the heating rate of 2 ℃/min, and preserving the heat for 4.5 hours to reduce the material to obtain a catalyst for synthesizing sorbitol; the time for dripping the ruthenium trichloride hydrochloric acid solution is 30min; the diluted hydrochloric acid may be 20% by mass, and the concentration of the diluted hydrochloric acid is not limited in this embodiment.
Example 8
The method for synthesizing sorbitol by using the catalysts of the embodiment 1 to 7 and the comparative embodiment 1 to 6 to catalyze the hydrogenation of glucose comprises the following steps:
step one, adding 100mL of 15 mass percent glucose aqueous solution and 0.3g of catalyst into a high-pressure reactor, introducing nitrogen to replace air in the high-pressure reactor, and replacing the nitrogen with hydrogen for 3 times;
step two, filling hydrogen into the high-pressure reactor with the nitrogen replaced for 3 times in the step one until the pressure is 3MPa, and reacting for 90min under the stirring condition at the temperature of 130 ℃ and the pressure of 3MPa to obtain a product;
and step three, filtering, and analyzing the filtrate by liquid chromatography, wherein the result is shown in table 1.
TABLE 1 catalytic sorbitol Synthesis reaction results
According to table 1, the conversion rate was 100% and the selectivity was 97% or more in the reaction for synthesizing sorbitol using the catalysts of examples 1 to 7, which shows that the catalyst for synthesizing sorbitol of the present invention has high catalytic activity and selectivity.
Example 9
In this embodiment, a method for synthesizing sorbitol by catalyzing the hydrogenation of glucose using the catalysts of embodiments 1 to 7 includes:
step one, adding 100mL of 20 mass percent glucose aqueous solution and 0.3g of catalyst into a high-pressure reactor, introducing nitrogen to replace air in the high-pressure reactor, and replacing the nitrogen with hydrogen for 3 times;
step two, filling hydrogen into the high-pressure reactor with the nitrogen replaced for 3 times in the step one until the pressure is 3.5MPa, and reacting for 70min under the stirring condition at the temperature of 110 ℃ and the pressure of 3.5MPa to obtain a product;
and step three, filtering, and analyzing the filtrate by liquid chromatography, wherein the result is shown in table 2.
TABLE 2 catalytic sorbitol Synthesis reaction results
According to table 2, in the reaction for synthesizing sorbitol by using the catalysts of examples 1 to 7, the conversion rate was 100% and the selectivity was 97% or more, which shows that the catalyst for synthesizing sorbitol of the present invention has high catalytic activity and selectivity.
Example 10
The method for synthesizing sorbitol by using the catalysts of examples 1 to 7 to catalyze the hydrogenation of glucose comprises the following steps:
step one, adding 100mL of 30 mass percent glucose aqueous solution and 0.3g of catalyst into a high-pressure reactor, introducing nitrogen to replace air in the high-pressure reactor, and replacing the nitrogen with hydrogen for 3 times;
step two, filling hydrogen into the high-pressure reactor with the nitrogen replaced for 3 times in the step one until the pressure is 4MPa, controlling the pressure to be 4MPa and the temperature to be 120 ℃ under the stirring condition, and reacting for 80min to obtain a product;
and step three, filtering, and analyzing the filtrate by liquid chromatography, wherein the result is shown in table 3.
TABLE 3 catalytic sorbitol Synthesis reaction results
According to table 3, in the reaction for synthesizing sorbitol by using the catalysts of examples 1 to 7, the conversion rate was 100% and the selectivity was 97% or more, which indicates that the catalyst for synthesizing sorbitol of the present invention has high catalytic activity and selectivity.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modifications, changes and equivalent structural changes made to the above embodiment according to the technical spirit of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (7)
1. The method for preparing the catalyst for synthesizing the sorbitol is characterized by comprising active carbon, ru and an auxiliary metal, wherein the Ru and the auxiliary metal are loaded on the active carbon, the mass percentage of the Ru in the catalyst is 3-4%, and the mass percentage of the auxiliary metal is 1-2%; the assistant metal comprises Ce and an assistant metal A, and the assistant metal A is La, mo, ga, yb or In; the mass of the Ce is 0.5-4 times of that of the assistant metal A;
the method comprises the following steps:
step one, mixing an aqueous solution containing an auxiliary agent metal soluble salt and sodium dodecyl sulfate with activated carbon, and stirring for 45-90 min to obtain a mixed system;
step two, dropwise adding an aqueous solution of a reducing agent into the mixed system obtained in the step one, and stirring for 12-24 hours after dropwise adding is finished to obtain activated carbon slurry containing an auxiliary metal;
thirdly, dropwise adding a ruthenium trichloride hydrochloric acid solution into the activated carbon slurry containing the auxiliary metal in the second step, stirring for 8-10 h after dropwise adding, drying, and reducing for 3-5 h by hydrogen to obtain a catalyst for synthesizing sorbitol;
the specific surface area of the pretreated active carbon in the step one is 1800m 2 /g～2000m 2 Activated carbon per gram, the method of pretreatment comprising:
step 101, setting the specific surface area to 600m 2 /g～650m 2/ Mixing g of activated carbon and a sodium bicarbonate aqueous solution, stirring for 20-30 h, and drying to obtain dried activated carbon;
step 102, in a nitrogen atmosphere, carrying out heat treatment on the dried activated carbon obtained in the step 101 in a tube furnace to obtain heat-treated activated carbon; the heat treatment is two-stage heat treatment, the temperature of the first stage heat treatment is 250-320 ℃, the heat preservation time is 1-2 h, the temperature of the second stage heat treatment is 760-850 ℃, and the heat preservation time is 2-3 h; in step 102, the temperature rising rate from the room temperature to the first stage heat treatment temperature is 2 ℃/min, and the temperature rising rate from the first stage heat treatment temperature to the second stage heat treatment temperature is 10 ℃/min;
and 103, washing the activated carbon subjected to the heat treatment in the step 102 to be neutral, and drying to obtain the pretreated activated carbon.
2. The method for preparing the catalyst for synthesizing the sorbitol according to claim 1, wherein the catalyst comprises active carbon, ru and an auxiliary metal, wherein the Ru and the auxiliary metal are loaded on the active carbon, and the mass percentage of the Ru in the catalyst is 3% -4%, and the mass percentage of the auxiliary metal is 1% -2%;
the auxiliary metal is Ce and auxiliary metal A, and the auxiliary metal A is La, mo, ga, yb or In.
3. The method for preparing the catalyst for synthesizing sorbitol according to claim 1 or 2, wherein the mass percentage of Ru in the catalyst is 4%, the mass percentage of the promoter metal is 1%, the mass percentage of the promoter metal is Ce and Mo, and the mass percentage of Ce and Mo are both 0.5%.
4. The method for preparing the catalyst for synthesizing sorbitol according to claim 1, wherein the mass percentage of the sodium bicarbonate aqueous solution in the step 101 is 5-20%.
5. The method for preparing the catalyst for synthesizing sorbitol according to claim 1, wherein in the aqueous solution containing the soluble salt of the auxiliary agent metal and sodium dodecyl sulfate in the first step, the mass of the sodium dodecyl sulfate is 5-10% of the mass of the auxiliary agent metal; the mass of the reducing agent in the second step is 4-8 times of that of the auxiliary metal in the first step, and the reducing agent is sodium borohydride, potassium borohydride or hydrazine hydrate; the dropping time of the aqueous solution of the reducing agent in the step two is 10-15 min; in the third step, the dripping time of the ruthenium trichloride hydrochloric acid solution is 30 min-60 min; in the third step, the hydrogen reduction is carried out in a tubular furnace, and the temperature of the hydrogen reduction is 400-600 ℃.
6. The method for preparing the catalyst for synthesizing sorbitol according to claim 5, wherein the stirring time in the first step is 60min; stirring for 24 hours in the step 101; the temperature of the first stage heat treatment in step 102 is 300 ℃ and the temperature of the second stage heat treatment is 800 ℃.
7. A method for synthesizing sorbitol by catalyzing glucose hydrogenation by using the catalyst obtained by the preparation method of claim 1, which comprises the following steps: reacting glucose aqueous solution with a catalyst in a hydrogen atmosphere of 3-4 MPa, wherein the reaction temperature is 110-130 ℃, and the reaction time is 70-90 min; the mass percentage content of the glucose aqueous solution is 15-30%, and the mass of the catalyst is 1-2% of the mass of glucose.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613253A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | The catalytic cracking method of a kind of sugar and sugar alcohol |
| CN102019185A (en) * | 2009-09-16 | 2011-04-20 | 中国科学院大连化学物理研究所 | Supported catalyst and application thereof in hydrocracking reaction of xylitol |
| KR20120110875A (en) * | 2011-03-30 | 2012-10-10 | 에쓰대시오일 주식회사 | Supported metal catalyst and method for selective catalytic conversion of cellulose to sorbitol in the presence of the catalyst |
| WO2015158634A1 (en) * | 2014-04-16 | 2015-10-22 | IFP Energies Nouvelles | Method for converting a feedstock including lignocellulosic biomass, using a homogeneous catalyst including a lanthanide in combination with a heterogeneous catalyst |
| CN105529192A (en) * | 2016-01-19 | 2016-04-27 | 湘潭大学 | Preparing method of copper quantum dot/activated carbon composite material applied to super capacitor |
| CN110028382A (en) * | 2019-03-28 | 2019-07-19 | 山东天力药业有限公司 | A method of preparing sorbierite |
| CN110743544A (en) * | 2019-11-07 | 2020-02-04 | 西安凯立新材料股份有限公司 | Palladium-carbon catalyst for preparing α -phenylethyl alcohol by selective hydrogenation of acetophenone and preparation method and application thereof |
| WO2020114287A1 (en) * | 2018-12-06 | 2020-06-11 | 浙江工业大学 | Ruthenium-nickel/activated carbon co-supported catalyst, preparation thereof and use thereof |
| CN111422871A (en) * | 2020-03-31 | 2020-07-17 | 大连理工大学 | Process for preparing high-quality activated carbon coproduction synthesis gas by multi-effect series negative pressure pyrolysis |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6720283B2 (en) * | 2002-01-03 | 2004-04-13 | Dalian Institute Of Chemical Physics | Activated carbon supported cobalt based catalyst for direct conversion of synthesis gas to diesel fuels |
| BR112012015933A2 (en) * | 2009-12-30 | 2018-07-24 | Virent Inc | method for converting oxygenated hydrocarbons to lower melecular weight oxygenated compounds, propylene glycol generation method and matter composition. |
| US20140162873A1 (en) * | 2012-07-11 | 2014-06-12 | South Dakota State University | Materials and methods for production of activated carbons |
| CA3023365A1 (en) * | 2016-05-30 | 2017-12-07 | Adven Industries, Inc. | Activated carbons with high surface areas and methods of making same |
-
2020
- 2020-09-21 CN CN202010995894.8A patent/CN112044433B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613253A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | The catalytic cracking method of a kind of sugar and sugar alcohol |
| CN102019185A (en) * | 2009-09-16 | 2011-04-20 | 中国科学院大连化学物理研究所 | Supported catalyst and application thereof in hydrocracking reaction of xylitol |
| KR20120110875A (en) * | 2011-03-30 | 2012-10-10 | 에쓰대시오일 주식회사 | Supported metal catalyst and method for selective catalytic conversion of cellulose to sorbitol in the presence of the catalyst |
| WO2015158634A1 (en) * | 2014-04-16 | 2015-10-22 | IFP Energies Nouvelles | Method for converting a feedstock including lignocellulosic biomass, using a homogeneous catalyst including a lanthanide in combination with a heterogeneous catalyst |
| CN105529192A (en) * | 2016-01-19 | 2016-04-27 | 湘潭大学 | Preparing method of copper quantum dot/activated carbon composite material applied to super capacitor |
| WO2020114287A1 (en) * | 2018-12-06 | 2020-06-11 | 浙江工业大学 | Ruthenium-nickel/activated carbon co-supported catalyst, preparation thereof and use thereof |
| CN110028382A (en) * | 2019-03-28 | 2019-07-19 | 山东天力药业有限公司 | A method of preparing sorbierite |
| CN110743544A (en) * | 2019-11-07 | 2020-02-04 | 西安凯立新材料股份有限公司 | Palladium-carbon catalyst for preparing α -phenylethyl alcohol by selective hydrogenation of acetophenone and preparation method and application thereof |
| CN111422871A (en) * | 2020-03-31 | 2020-07-17 | 大连理工大学 | Process for preparing high-quality activated carbon coproduction synthesis gas by multi-effect series negative pressure pyrolysis |
Non-Patent Citations (2)
| Title |
|---|
| 李万刚等.钌系催化剂在不饱和化合物选择性加氢中的应用.《江西科学》.2004, * |
| 钌系催化剂在不饱和化合物选择性加氢中的应用;李万刚等;《江西科学》;20040630;第151-152页 * |
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