CN112044433A - Catalyst for synthesizing sorbitol and preparation method and application thereof - Google Patents

Catalyst for synthesizing sorbitol and preparation method and application thereof Download PDF

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CN112044433A
CN112044433A CN202010995894.8A CN202010995894A CN112044433A CN 112044433 A CN112044433 A CN 112044433A CN 202010995894 A CN202010995894 A CN 202010995894A CN 112044433 A CN112044433 A CN 112044433A
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catalyst
activated carbon
metal
auxiliary metal
temperature
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CN112044433B (en
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颜攀敦
朱露露
张洁兰
陈丹
牟博
张波波
李岳锋
万克柔
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Kaili Catalyst New Materials Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • 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
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • 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
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6525—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • 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

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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

Catalyst for synthesizing sorbitol and preparation method and application thereof
Technical Field
The invention belongs to the technical field of noble metal catalysts, and particularly relates to a catalyst for synthesizing sorbitol, and 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 novel 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 uses it as catalyst to prepare sorbierite by catalytic hydrogenation of glucose, the conversion rate can reach 100%, but the selectivity is only 93.3%. Chinese patent application publication No. 201710757968.2, published as 12 and 15 in 2017, discloses a method for hydrogenating glucose with a semi-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 well separated 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 1800m2/g～2000m2/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 1800m2/g～2000m2Activated carbon per gram, the method of pretreatment comprising:
step 101, setting the specific surface area to 600m2/g～650m2Mixing 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 60 min; 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 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.
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 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 600m2Mixing 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 1 wt% by mass 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 1 wt% in mass percentage to obtain pretreated activated carbon; the specific surface area of the pretreated activated carbon is 1800m2/g；
Step four, 0.3098g Ce (NO)3)3.6H2O、0.3118g La(NO3)3.6H2Dissolving O and 0.01g of lauryl sodium sulfate by using 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 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 10 min;
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 1 wt%, 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 a catalyst for synthesizing sorbitol; dripping ruthenium trichloride hydrochloric acid solution for 30 min; 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 600m2The 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 commercial specific surface area was 1800m2The 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 650m2Mixing the activated carbon per gram with 300mL of a sodium bicarbonate aqueous solution with the mass percentage of 10%, stirring for 24 hours at normal temperature, and drying until the water content is lower than 1 wt% 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 2 h; 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 1 wt% in mass percentage to obtain pretreated activated carbon; the specific surface area of the pretreated activated carbon is 1890m2/g；
Step four, 0.1549g Ce (NO)3)3.6H2O、0.2525g GaCl3And 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 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 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 10 min;
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 1 wt%, 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 reducing the material by keeping the temperature for 4.5 hours to obtain a catalyst for synthesizing sorbitol; the time for dripping the ruthenium trichloride hydrochloric acid solution is 45 min; 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 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 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 625m2Mixing 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 1 wt% 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 1 wt% in mass percentage to obtain pretreated activated carbon; the specific surface area of the pretreated activated carbon is 2000m2/g；
Step four, 0.1549g Ce (NO)3)3.6H2O、0.1021g(NH4)2MoO4And 0.01g of sodium dodecyl sulfate is dissolved by 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 15 min;
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 1 wt%, 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 preserving the heat for 3 hours to reduce the material to obtain a catalyst for synthesizing sorbitol; dripping ruthenium trichloride hydrochloric acid solution for 50 min; 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 is Ce and 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, setting the specific surface area of 30g to 650m2Mixing activated carbon per gram with 300mL of a sodium bicarbonate aqueous solution with the mass percentage of 15%, stirring for 24 hours at normal temperature, and drying until the water content is lower than 1 wt% 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 1 wt% in mass percentage to obtain pretreated activated carbon; the specific surface area of the pretreated activated carbon is 1900m2/g；
Step four, 0.2127g of CeCl3.6H2O、0.0323g YbCl3And 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 10 min;
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 1 wt%, putting the dried material into a tubular furnace with hydrogen as an atmosphere, raising the temperature to 550 ℃ at the heating rate of 2 ℃/min, and preserving the heat for 3.5 hours to reduce the material to obtain a catalyst for synthesizing sorbitol; the time for dripping the ruthenium trichloride hydrochloric acid solution is 60 min; 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 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 645m2Mixing per gram of activated carbon 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 mass percentage content of water is lower than 1 wt% 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 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 1 wt% in mass percentage to obtain pretreated activated carbon; the specific surface area of the pretreated activated carbon is 1860m2/g；
Step four, 0.4957gCe (NO)3)2.6H2O、0.0771g InCl3And 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 12 min;
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 1 wt%, 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 50 min; 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 620m2Mixing the activated carbon per gram with 300mL of a 5% sodium bicarbonate aqueous solution by mass, stirring for 20 hours at normal temperature, and drying until the water content is lower than 1 wt% 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 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 1 wt% in mass percentage to obtain pretreated activated carbon; the specific surface area of the pretreated activated carbon is 1800m2/g；
Step four, 0.3098g Ce (NO)3)3.6H2O、0.3118g La(NO3)3.6H2Dissolving O and 0.01g of lauryl sodium sulfate by using 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 auxiliary agent metal; the reducing agent is sodium borohydride, and the time for dripping the aqueous solution of the reducing agent is 10 min;
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 1 wt%, 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 30 min; the dilute hydrochloric acid may be 20% by weight, and the concentration of the dilute 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 630m2Mixing 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 1 wt% 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 1 wt% in mass percentage to obtain pretreated activated carbon; the specific surface area of the pretreated activated carbon is 1800m2/g；
Step four, 0.3098g Ce (NO)3)3.6H2O、0.3118g La(NO3)3.6H2Dissolving O and 0.01g of lauryl sodium sulfate by using 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 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 10 min;
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 1 wt%, 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 30 min; the dilute hydrochloric acid may be 20% by weight, and the concentration of the dilute hydrochloric acid is not limited in this embodiment.
Example 8
The method for synthesizing sorbitol by using the catalysts of examples 1 to 7 and comparative examples 1 to 6 to catalyze glucose hydrogenation 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
Figure BDA0002692510350000151
Figure BDA0002692510350000161
According to table 1, in the reaction for synthesizing sorbitol by using the catalysts of examples 1 to 7, the conversion rate is 100%, and the selectivity is more than 97%, which shows that the catalyst for synthesizing sorbitol has high catalytic activity and selectivity.
Example 9
In this embodiment, the method for synthesizing sorbitol by hydrogenating glucose using the catalyst 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
Figure BDA0002692510350000162
Figure BDA0002692510350000171
According to table 2, in the reaction for synthesizing sorbitol by using the catalysts of examples 1 to 7, the conversion rate is 100%, and the selectivity is more than 97%, which shows that the catalyst for synthesizing sorbitol has high catalytic activity and selectivity.
Example 10
In this embodiment, the method for synthesizing sorbitol by hydrogenating glucose using the catalyst of embodiments 1 to 7 includes:
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, and reacting for 80min under the stirring condition at the temperature of 120 ℃ and the pressure of 4MPa 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
Figure BDA0002692510350000172
According to table 3, in the reaction for synthesizing sorbitol by using the catalysts of examples 1 to 7, the conversion rate is 100%, and the selectivity is more than 97%, which shows that the catalyst for synthesizing sorbitol 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 all 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 (10)

1. 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.
2. The catalyst for synthesizing the sorbitol according to claim 1, which 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.
3. The catalyst for synthesizing sorbitol according to claim 1 or 2, wherein the mass of Ce is 0.5-4 times of that of the assistant metal A; the specific surface area of the activated carbon is 1800m2/g～2000m2/g。
4. 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 auxiliary metal is 1%, the mass percentage of the auxiliary metal is Ce and Mo, and the mass percentage of Ce and Mo are both 0.5%.
5. A method for preparing the catalyst for synthesizing sorbitol according to claim 1, comprising the steps of:
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.
6. The method of claim 5, wherein the activated carbon in step one has a pre-treated specific surface area of 1800m2/g～2000m2Activated carbon per gram, the method of pretreatment comprising:
step 101, setting the specific surface area to 600m2/g～650m2Mixing 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.
7. The method according to claim 6, wherein the sodium bicarbonate aqueous solution in step 101 is 5-20% by weight; 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.
8. The method according to any one of claims 5 to 7, wherein in the aqueous solution containing the assistant metal soluble salt and the sodium dodecyl sulfate in the first step, the mass of the sodium dodecyl sulfate is 5 to 10 percent 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 ℃.
9. The method of claim 6, wherein the stirring time in step one is 60 min; 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 ℃.
10. A method for synthesizing sorbitol by using the catalyst of claim 1 to catalyze the hydrogenation of glucose, comprising: 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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