CN113233961A - Method for preparing sugar alcohol by catalytic hydrogenation - Google Patents
Method for preparing sugar alcohol by catalytic hydrogenation Download PDFInfo
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- CN113233961A CN113233961A CN202110532798.4A CN202110532798A CN113233961A CN 113233961 A CN113233961 A CN 113233961A CN 202110532798 A CN202110532798 A CN 202110532798A CN 113233961 A CN113233961 A CN 113233961A
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- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title claims abstract description 23
- 150000005846 sugar alcohols Chemical class 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 126
- 239000003054 catalyst Substances 0.000 claims abstract description 109
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 106
- 239000000243 solution Substances 0.000 claims abstract description 92
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- 239000008103 glucose Substances 0.000 claims abstract description 60
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000706 filtrate Substances 0.000 claims abstract description 31
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- 238000004448 titration Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 28
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
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- 239000011668 ascorbic acid Substances 0.000 claims description 2
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
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- 239000012279 sodium borohydride Substances 0.000 claims description 2
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 abstract description 16
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 31
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- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
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- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical class [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
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- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 description 1
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- 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
- C07C29/136—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 of >C=O containing groups, e.g. —COOH
- C07C29/14—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 of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—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 of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
-
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for preparing sugar alcohol by catalytic hydrogenation, belonging to the method for preparing sugar alcohol. Adding a ruthenium-carbon catalyst and a glucose solution into a hydrogenation high-pressure reaction kettle, then replacing air in the kettle, carrying out hydrogenation operation at a certain temperature in a constant-pressure mode, taking out a mixed solution containing the catalyst at a certain temperature after the reaction is finished, recovering the catalyst for next cycle after filtering, and analyzing the composition and the conversion rate of the reaction filtrate by adopting a reducing sugar titration method and a liquid chromatography method after the reaction filtrate is recovered. The method adopts the ruthenium-carbon catalyst, achieves the aim of preparing the sorbitol with high conversion rate and high selectivity by controlling reaction temperature, pressure, stirring speed and operation conditions, and has the advantages of high conversion rate, high selectivity, simple operation, mild reaction conditions, improved safety, low energy consumption, low production cost, small equipment maintenance and investment and the like.
Description
Technical Field
The invention relates to a method for preparing sugar alcohol, which is especially suitable for preparing corresponding sugar alcohol by hydrogenation of saccharides containing carbonyl compounds, in particular for preparing sorbitol by catalytic hydrogenation of glucose.
Background
Sorbitol is white crystalline powder at room temperature, has certain hygroscopicity, can be dissolved in water and organic solution such as propylene glycol, and has certain heat resistance. The sorbitol is widely applied to printing, textile, daily chemical, food and pharmaceutical industries, and is used as a medical intermediate, a high-added-value fine chemical product, and the production of vitamin C in the pharmaceutical industry is large. Not only is the main product of sorbitol isomerization, such as isosorbide, relatively high in added value. And the method for preparing C2 and C3 low-polyol by decomposing biomass sorbitol has certain advantages compared with the method for preparing C2 and C3 low-polyol by cracking non-renewable energy petroleum.
The prior production process of sorbitol mainly comprises the following three processes: respectively a microbial fermentation method, an electrolysis method and a catalytic hydrogenation method. The microbial fermentation method has the disadvantages of complex operation and relatively high cost, and has certain difficulty in being applied to large-scale industrial production. The electrolytic reduction method mainly uses glucose as a basic raw material, and adds a certain reducing agent to generate the sorbitol in an electrolytic manner. However, the conversion rate of glucose is low, byproducts are generated, and the production cost is relatively high due to high power consumption, so that the method cannot be applied to the large-scale production of sorbitol at present.
Currently, the large-scale industrial production of sorbitol is mainly prepared by a glucose catalytic hydrogenation method, and the main difference of different process routes is that the catalyst for catalytic hydrogenation is different and the hydrogenation mode is different. At present, the domestic hydrogenation catalyst generally adopts modified Raney-Ni catalyst and ruthenium carbon catalyst. The hydrogenation mode mainly comprises an intermittent hydrogenation process and a continuous hydrogenation process. When the Raney-Ni catalyst is applied to glucose hydrogenation, not only is the reaction temperature and pressure high, but also side reactions exist, active components of the catalyst can be lost, the loss of the active components Ni can cause the activity of the catalyst to be reduced, and part of the lost active components Ni enters the product hydrogenation liquid and exists in the hydrogenation liquid in the form of Ni ions, so that the product purity is reduced, if a high-purity product is obtained, a separation working section is required to be added, certain difficulty is brought to the purification of the subsequent hydrogenation product components, and the production cost is increased. The method is characterized in that active carbon and the like are used as carriers to load metal ruthenium to be used as hydrogenation catalysts in foreign countries, the catalysts have the advantages of high activity and selectivity and the like, the reaction conditions are mild, the safety performance is improved relatively, the requirements on equipment are low, and part of equipment investment can be saved for newly-built process equipment, so that the production cost is reduced. Most importantly, the ruthenium catalyst can resist certain weak acidity, and the reaction active components can not be dissolved in the reaction liquid, so that the separation and purification difficulty of the post-treatment hydrogenation product is reduced, and part of the cost expenditure is reduced. The process flow is simplified while the process operation cost is reduced, and the method is suitable for large-scale production.
For the catalytic hydrogenation mode, the continuous hydrogenation method has the following advantages: the continuous method generally adopts a slurry type or fixed bed reactor, can realize large-scale continuous production, and has the defects of long construction period, high equipment investment, higher pressure required by the reaction, and high pressure reaction of more than 10 MPa.
The catalytic hydrogenation by the batch method has the advantages of simple process, mature preparation route, mild reaction conditions, short preparation flow, short construction period and relatively small equipment investment, but has the disadvantages of relatively low automation degree, and the increase of equipment investment and labor cost caused by increasing a plurality of parallel equipment in unit time for increasing the yield. But compared with the continuous method, the reaction conditions are milder, and the pressure required by the reaction is reduced.
Glucose hydrogenation catalysts generally have the problems of low glucose conversion rate, incomplete hydrogenation, side reaction, low selectivity, loss of active components of the catalysts and the like.
Disclosure of Invention
The invention provides a method for preparing sugar alcohol by catalytic hydrogenation, aiming at solving the technical problems of how to efficiently carry out catalytic hydrogenation on glucose, improving the conversion rate of glucose and the selectivity of sorbitol, reducing the production energy consumption, saving the cost and simultaneously not polluting the environment. The ruthenium-carbon catalyst realizes high-efficiency hydrogenation, and solves the problems of environmental pollution and convenient storage of the catalyst.
The technical scheme adopted by the invention is as follows: comprises the following steps:
(1) firstly, dissolving glucose at 50-60 ℃, wherein the mass concentration is 40-55%, and the total mass is 400 g;
(2) adding a ruthenium-carbon catalyst into a high-pressure hydrogenation reaction kettle with an effective volume of 1L, and then adding the sugar liquid obtained in the step (1), wherein the mass ratio of the added amount of the ruthenium-carbon catalyst to the dry sugar is preferably 4-6.5%;
(3) firstly introducing N into a sealed reaction kettle2Replacing air in the kettle for 3-5 times, and then continuously introducing N2Completely replacing the air in the kettle for 5-10 min;
(4) switching gas source to H2Then, H is introduced first2Replacing air in the kettle for 3-5 times, and then continuously introducing H25-10 min to completely replace N in the kettle2；
(5) Raising the stirring speed to 700-1200 rpm/min, then raising the temperature to 80-130 ℃, controlling the pressure to be raised to 2.5-4.5 MPa, turning off the heating power supply when the temperature reaches a set value, and continuously introducing H at the moment2Maintaining a constant voltage mode;
(6) when the reaction is finished, controlling the temperature of the reaction materials discharged from the kettle to be 50-120 ℃;
(7) and (3) taking out the hydrogenation solution, carrying out negative pressure filtration, recovering the catalyst for next cycle use, recovering the hydrogenation filtrate to a certain volume, and carrying out a reducing sugar titration test and High Performance Liquid Chromatography (HPLC) analysis.
The mass concentration of the glucose solution in the step (1) is 50%.
The mass ratio of the added mass of the ruthenium-carbon catalyst in the step (2) to the mass of glucose liquid is 1: 40.
the ruthenium carbon catalyst in the step (2) is prepared by the following steps:
1) weighing 200-300 meshes, and the specific surface area is 1000-2000 m2Adding the powder active carbon per gram into a three-neck flask or a beaker; adding ultrapure water into activated carbon, wherein the volume weight ratio of the ultrapure water to the activated carbon is V(Water)：m(activated carbon)Stirring at a low speed of 2-14, adding a ruthenium-containing Ru precursor compound into the carbon slurry solution, adjusting the pH value of the solution to obtain a dipping mixed solution of the ruthenium-containing carbon solution,
2) dipping the dipping mixed solution containing the ruthenium-carbon solution for 45 min-3 h, and then adjusting the pH value of the dipping mixed solution to 10-11 again;
3) adding a reducing agent, wherein the molar ratio of the reducing agent to Ru atoms is 1: 1, preparing a solution with the same volume as the impregnation mixed solution, adding the solution into the step (2), and rapidly increasing the stirring speed to 450-500 rpm/min, wherein the reduction time is 1-2 h, and the reduction temperature is 10-30 ℃;
4) after reduction, removing the impregnation liquid by adopting a positive pressure filtration mode, then washing the catalyst solid powder to be neutral by adopting ultrapure water, obtaining the ruthenium-carbon catalyst after filtration, and sealing and storing at room temperature for later use, wherein the electric conductivity is less than 20 mu s/cm.
The ruthenium content is 0.5-5% by mass.
In the step 1), the precursor compound containing ruthenium Ru is chlorine-containing ruthenium salt.
The pH value of the dipping mixed solution of the ruthenium-containing carbon solution in the step 1) is 0.8-7.
The dipping temperature of the dipping mixed solution of the ruthenium-containing carbon solution in the step 2) is 10-30 ℃.
The reducing agent in the step 3) adopts methanol, ethanol, glycol, ascorbic acid AA and potassium borohydride KBH4Or sodium borohydride.
The invention firstly adopts the high-activity ruthenium carbon catalyst, controls the average size of ruthenium (Ru) nano particles to be 2.9nm, controls the ruthenium load capacity on an active carbon carrier to be 0.5-5%, then the product purity and the glucose conversion rate are controlled and optimized by a high-pressure reaction kettle intermittent hydrogenation and variable-temperature constant-pressure hydrogenation process, an isometric reduction method is adopted in the method, the concentration of a reducing agent is reduced after the reducing agent is prepared into an isometric volume, the contact probability of the reducing agent and ruthenium ions is reduced, the quantity of instantly generated ruthenium nano-particles is reduced, the aggregation of a large quantity of Ru nano-particles is prevented, and the high-speed stirring frequency also enables the generated Ru nano particles to be transferred quickly, reduces the collision chance with the newly generated Ru nano particles, thereby slowing down the growth of Ru crystal grains, because the reduced ruthenium nano-particles are bound by the pore diameter of the carrier, the migration length of the reduced ruthenium nano-particles is limited, and the effect of stabilizing the Ru nano-particles is achieved.
The ruthenium-carbon catalyst adopted by the invention is obtained by adopting an isometric liquid phase reduction method to obtain the catalyst with high activity and high selectivity, and can be stored under the condition of room temperature and air, the method has the advantages of simple operation, high reproducibility and the like, the active component ruthenium nano particles have uniform size, small particle size and high catalytic activity, particularly, the catalytic hydrogenation process condition is mild in the reaction process of preparing sorbitol by glucose hydrogenation, the advantages of high glucose conversion rate, high sorbitol selectivity and the like are reflected, the energy consumption and the production cost are reduced while the product quality is regulated and controlled by controlling the catalytic hydrogenation mode and optimizing the production process parameters, and the operation safety is improved.
Drawings
FIG. 1 is a transmission electron microscope photograph of a ruthenium carbon catalyst according to the present invention before use;
as can be seen from FIG. 1, the catalyst has better dispersibility, the metal agglomeration phenomenon is not obvious, and the metal active component particles are more dispersed;
FIG. 2 is a transmission electron microscope photograph of a ruthenium carbon catalyst after use in accordance with the invention;
as can be seen from fig. 2, the catalyst has no obvious particle change after use, the catalyst carrier has no specific change, and the whole catalyst has certain stability;
fig. 3 is a catalyst XRD pattern of the activated carbon-supported ruthenium nanoparticles of the present invention;
it can be seen from fig. 3 that the prepared catalyst has good dispersibility, and the ruthenium nanoparticles are dispersed on the activated carbon support;
FIG. 4 is a graph of glucose conversion according to the present invention;
as can be seen from FIG. 4, the catalyst can be recycled 28 times, each time under the same catalytic hydrogenation conditions, the complete conversion of glucose can be achieved, and the conversion rate can reach 100%.
Detailed Description
The present invention will be further described below by way of specific embodiments, which are different in catalyst loading, hydrogenation temperature, hydrogenation pressure, reactor outlet temperature, and hydrogenation process, as compared to the prior art, and therefore the examples will be selected from these points.
In the following scheme, an X-ray diffractometer (XRD) and a Transmission Electron Microscope (TEM) are adopted to measure the change condition of the catalyst before and after the reaction, a high-pressure hydrogenation reaction kettle is adopted to prepare a sorbitol solution, and the content and the conversion rate of a reaction product are analyzed by a reducing sugar titration method and a high performance liquid chromatography. The specific test conditions are that the dosage of the fixed catalyst is 10g and the mass of the glucose solution is 400g (50%), and the whole reaction process is controlled by adjusting the reaction temperature, the reaction pressure and the temperature of the reaction materials out of the kettle to control the whole reaction time.
Example 1
Weighing 10g (dry basis) of 200-300 meshes and specific surface area of 1040m2The/g is catalyst carrier material.
The following are examples of the preparation of 1% loading ruthenium carbon catalysts:
36.6mM RuCl was weighed3 .xH2O27.03 mL (Ru content is more than or equal to 37 percent) and a proper amount of ultrapure water (V)(ultrapure water)：m(Carrier)14). First, 10g of activated carbon support (m for 1% loading) was added to a three-necked flat-bottomed flask(Ru):m(Ru + charcoal)1%) was added to the solution, and then 140mL of ultrapure water was added, followed by stirring for 5 minutes, and then the ruthenium-containing solution was added, and the solution was immersed at room temperature for 3 hours while adjusting the pH to 1, to obtain a ruthenium-containing adsorption solution. Adding appropriate amount of reducing agent into the solution to obtain an equal volume solution, adding, stirring, reducing for 1 hr to obtain a solution with pH>9, washing the catalyst to be neutral after the reduction is finished, and packaging for later use. Other loadings such as 0.5% (m)(Ru):m(Ru + charcoal)＝0.5％)、2％(m(Ru):m(Ru + charcoal)＝2％)、2.5％(m(Ru):m(Ru + charcoal)＝2.5％)、5％(m(Ru):m(Ru + charcoal)5%) and the like were prepared in this manner.
Example 2
10g (dry basis) of the ruthenium on carbon catalyst prepared in example 1 were weighed out. Preparing 400g of 50% glucose solution (m)(catalyst)：m(sugar solution)＝1：40)。
Firstly, adding 10g of 0.5% loading ruthenium-carbon catalyst (Ru/AC) into a high-pressure hydrogenation reaction kettle with an effective volume of 1L, then adding a dissolved glucose solution into the reaction kettle, sealing the reaction kettle, firstly performing nitrogen replacement for 3-5 times, and then continuously introducing nitrogen for about 5-10 min to perform nitrogen replacement so as to ensure thorough air replacement in the reaction kettle; and then, switching to hydrogen replacement for 3-5 times, and continuously introducing hydrogen for replacement for about 5-10 min to ensure that the nitrogen in the reaction kettle is replaced thoroughly. After the replacement is finished, the pressure in the kettle is increased to 4MPa, the rotating speed is controlled to be 1000rpm/min, then the reaction temperature is increased to 106 ℃, hydrogenation is carried out by adopting a variable-temperature continuous hydrogen-introduction constant-pressure mode, the temperature of the material discharged from the kettle is controlled to be 50 ℃, after the hydrogenation liquid is taken out, negative pressure filtration is firstly carried out, the catalyst is recovered for next cycle use, and after the hydrogenation filtrate is recovered, the volume is fixed to 1L, and then the content analysis of reducing sugar is carried out.
Example 3
10g (dry basis) of the self-prepared ruthenium on carbon catalyst were weighed. Preparing a 50% glucose solution, 400g (m)(catalyst)：m(sugar solution)＝1：40)。
Firstly, adding 10g of ruthenium-carbon catalyst (Ru/AC) with 1% loading capacity into a high-pressure hydrogenation reaction kettle with an effective volume of 1L, then adding a dissolved glucose solution into the reaction kettle, sealing the reaction kettle, firstly performing nitrogen replacement for 3-5 times, and then continuously introducing nitrogen for about 5-10 min for nitrogen replacement to ensure that the air in the reaction kettle is completely replaced; and then, switching to hydrogen replacement for 3-5 times, and continuously introducing hydrogen for replacement for about 5-10 min to ensure that the nitrogen in the reaction kettle is replaced thoroughly. After the replacement is finished, the pressure in the kettle is increased to 4MPa, the rotating speed is controlled at 1000rpm/min, then the reaction temperature is increased to 106 ℃, the hydrogenation is carried out by adopting a variable-temperature intermittent hydrogen-introduction non-constant-pressure mode, and the temperature of the material discharged from the kettle is controlled at 50 ℃. And (3) after the hydrogenation solution is taken out, firstly, carrying out negative pressure filtration, recovering the catalyst for next cycle use, and carrying out reducing sugar content analysis after the volume of the hydrogenation filtrate is determined to 1L after the hydrogenation filtrate is recovered.
Example 4
10g (dry basis) of the self-prepared ruthenium on carbon catalyst were weighed. Preparing a 50% glucose solution, 400g (m)(catalyst)：m(sugar solution)＝1：40)。
Firstly, adding 10g of ruthenium-carbon catalyst (Ru/AC) with 2% loading capacity into a high-pressure hydrogenation reaction kettle with an effective volume of 1L, then adding a dissolved glucose solution into the reaction kettle, sealing the reaction kettle, firstly performing nitrogen replacement for 3-5 times, and then continuously introducing nitrogen for about 5-10 min for nitrogen replacement to ensure that the air in the reaction kettle is completely replaced; and then, switching to hydrogen replacement for 3-5 times, and continuously introducing hydrogen for replacement for about 5-10 min to ensure that the nitrogen in the reaction kettle is replaced thoroughly. After the replacement is finished, the pressure in the kettle is increased to 4MPa, the rotating speed is controlled at 800rpm/min, then the reaction temperature is increased to 106 ℃, hydrogenation is carried out by adopting a variable-temperature continuous hydrogen-introduction constant-pressure mode, and the temperature of the material discharged from the kettle is controlled at 70 ℃. And (3) after the hydrogenation solution is taken out, firstly, carrying out negative pressure filtration, recovering the catalyst for next cycle use, and carrying out reducing sugar content analysis after the volume of the hydrogenation filtrate is determined to 1L after the hydrogenation filtrate is recovered.
Example 5
10g (dry basis) of the self-prepared ruthenium on carbon catalyst were weighed. Preparing a 50% glucose solution, 400g (m)(catalyst)：m(sugar solution)＝1：40)。
Firstly, adding 10g of 2.5% loading ruthenium-carbon catalyst (Ru/AC) into a high-pressure hydrogenation reaction kettle with an effective volume of 1L, then adding a dissolved glucose solution into the reaction kettle, sealing the reaction kettle, firstly performing nitrogen replacement for 3-5 times, and then continuously introducing nitrogen for about 5-10 min for nitrogen replacement to ensure that the air in the reaction kettle is completely replaced; and then, switching to hydrogen replacement for 3-5 times, and continuously introducing hydrogen for replacement for about 5-10 min to ensure that the nitrogen in the reaction kettle is replaced thoroughly. After the replacement is finished, the pressure in the kettle is increased to 4MPa, the rotating speed is controlled at 1000rpm/min, then the reaction temperature is increased to 106 ℃, the hydrogenation is carried out by adopting a variable-temperature continuous hydrogen-introduction constant-pressure mode, and the temperature of the material discharged from the kettle is controlled at 70 ℃. And (3) after the hydrogenation solution is taken out, firstly, carrying out negative pressure filtration, recovering the catalyst for next cycle use, and carrying out reducing sugar content analysis after the volume of the hydrogenation filtrate is determined to 1L after the hydrogenation filtrate is recovered.
Example 6
10g (dry basis) of the self-prepared ruthenium on carbon catalyst were weighed. Preparing a 50% glucose solution, 400g (m)(catalyst)：m(sugar solution)＝1：40)。
Firstly, adding 10g of 5% loading ruthenium-carbon catalyst (Ru/AC) into a high-pressure hydrogenation reaction kettle with an effective volume of 1L, then adding a dissolved glucose solution into the reaction kettle, sealing the reaction kettle, firstly performing nitrogen replacement for 3-5 times, and then continuously introducing nitrogen for about 5-10 min for nitrogen replacement to ensure that air in the reaction kettle is completely replaced; and then, switching to hydrogen replacement for 3-5 times, and continuously introducing hydrogen for replacement for about 5-10 min to ensure that the nitrogen in the reaction kettle is replaced thoroughly. After the replacement is finished, the pressure in the kettle is increased to 4MPa, the rotating speed is controlled at 1000rpm/min, then the reaction temperature is increased to 106 ℃, the hydrogenation is carried out by adopting a variable-temperature continuous hydrogen-introduction constant-pressure mode, and the temperature of the material discharged from the kettle is controlled at 50 ℃. And (3) after the hydrogenation solution is taken out, firstly, carrying out negative pressure filtration, recovering the catalyst for next cycle use, and carrying out reducing sugar content analysis after the volume of the hydrogenation filtrate is determined to 1L after the hydrogenation filtrate is recovered.
Example 7
10g (dry basis) of the self-prepared ruthenium on carbon catalyst were weighed. Preparing a 50% glucose solution, 400g (m)(catalyst)：m(sugar solution)＝1：40)。
Firstly, adding 10g of ruthenium-carbon catalyst (Ru/AC) with 1% loading capacity into a high-pressure hydrogenation reaction kettle with an effective volume of 1L, then adding a dissolved glucose solution into the reaction kettle, sealing the reaction kettle, firstly performing nitrogen replacement for 3-5 times, and then continuously introducing nitrogen for about 5-10 min for nitrogen replacement to ensure that the air in the reaction kettle is completely replaced; and then, switching to hydrogen replacement for 3-5 times, and continuously introducing hydrogen for replacement for about 5-10 min to ensure that the nitrogen in the reaction kettle is replaced thoroughly. After the replacement is finished, the pressure in the kettle is increased to 4MPa, the rotating speed is controlled at 1000rpm/min, then the reaction temperature is increased to 75 ℃, the hydrogenation is carried out by adopting a variable-temperature continuous hydrogen-introduction constant-pressure mode, and the temperature of the material discharged from the kettle is controlled at 70 ℃. And (3) after the hydrogenation solution is taken out, firstly, carrying out negative pressure filtration, recovering the catalyst for next cycle use, and carrying out reducing sugar content analysis after the volume of the hydrogenation filtrate is determined to 1L after the hydrogenation filtrate is recovered.
Example 8
10g (dry basis) of the self-prepared ruthenium on carbon catalyst were weighed. Preparing a 50% glucose solution, 400g (m)(catalyst)：m(sugar solution)＝1：40)。
Firstly, adding 10g of 2% ruthenium-carbon catalyst (Ru/AC) into a high-pressure hydrogenation reaction kettle with an effective volume of 1L, then adding a dissolved glucose solution into the reaction kettle, sealing the reaction kettle, firstly performing nitrogen replacement for 3-5 times, and then continuously introducing nitrogen for about 5-10 min for nitrogen replacement to ensure that air in the reaction kettle is completely replaced; and then, switching to hydrogen replacement for 3-5 times, and continuously introducing hydrogen for replacement for about 5-10 min to ensure that the nitrogen in the reaction kettle is replaced thoroughly. After the replacement is finished, the pressure in the kettle is increased to 4MPa, the rotating speed is controlled at 1000rpm/min, then the reaction temperature is increased to 80 ℃, the hydrogenation is carried out by adopting a variable-temperature continuous hydrogen-introduction constant-pressure mode, and the temperature of the material discharged from the kettle is controlled at 70 ℃. And (3) after the hydrogenation solution is taken out, firstly, carrying out negative pressure filtration, recovering the catalyst for next cycle use, and carrying out reducing sugar content analysis after the volume of the hydrogenation filtrate is determined to 1L after the hydrogenation filtrate is recovered.
Example 9
10g (dry basis) of the self-prepared ruthenium on carbon catalyst were weighed. Preparing a 50% glucose solution, 400g (m)(catalyst)：m(sugar solution)＝1：40)。
Firstly, adding 10g of 1% ruthenium-carbon catalyst (Ru/AC) into a high-pressure hydrogenation reaction kettle with an effective volume of 1L, then adding a dissolved glucose solution into the reaction kettle, sealing the reaction kettle, firstly performing nitrogen replacement for 3-5 times, and then continuously introducing nitrogen for about 5-10 min for nitrogen replacement to ensure that air in the reaction kettle is completely replaced; and then, switching to hydrogen replacement for 3-5 times, and continuously introducing hydrogen for replacement for about 5-10 min to ensure that the nitrogen in the reaction kettle is replaced thoroughly. After the replacement is finished, the pressure in the kettle is increased to 4MPa, the rotating speed is controlled at 1000rpm/min, then the reaction temperature is increased to 90 ℃, hydrogenation is carried out by adopting a variable-temperature intermittent hydrogen introduction mode, and the temperature of the material discharged from the kettle is controlled at 70 ℃.
Example 10
10g (dry basis) of the self-prepared ruthenium on carbon catalyst were weighed. Preparing a 50% glucose solution, 400g (m)(catalyst)：m(sugar solution)＝1：40)。
Firstly, adding 10g of 1% ruthenium-carbon catalyst (Ru/AC) into a high-pressure hydrogenation reaction kettle with an effective volume of 1L, then adding a dissolved glucose solution into the reaction kettle, sealing the reaction kettle, firstly performing nitrogen replacement for 3-5 times, and then continuously introducing nitrogen for about 5-10 min for nitrogen replacement to ensure that air in the reaction kettle is completely replaced; and then, switching to hydrogen replacement for 3-5 times, and continuously introducing hydrogen for replacement for about 5-10 min to ensure that the nitrogen in the reaction kettle is replaced thoroughly. After the replacement is finished, the pressure in the kettle is increased to 3.5MPa, the rotating speed is controlled at 1000rpm/min, then the reaction temperature is increased to 85 ℃, the hydrogenation is carried out by adopting a variable-temperature continuous hydrogen-introduction constant-pressure mode, and the temperature of the material discharged from the kettle is controlled at 70 ℃. And (3) after the hydrogenation solution is taken out, firstly, carrying out negative pressure filtration, recovering the catalyst for next cycle use, and carrying out reducing sugar content analysis after the volume of the hydrogenation filtrate is determined to 1L after the hydrogenation filtrate is recovered.
Example 11
10g (dry basis) of the self-prepared ruthenium on carbon catalyst were weighed. Preparing a 50% glucose solution, 400g (m)(catalyst)：m(sugar solution)＝1：40)。
Firstly, adding 10g of ruthenium-carbon catalyst (Ru/AC) with 1% loading capacity into a high-pressure hydrogenation reaction kettle with an effective volume of 1L, then adding a dissolved glucose solution into the reaction kettle, sealing the reaction kettle, firstly performing nitrogen replacement for 3-5 times, and then continuously introducing nitrogen for about 5-10 min for nitrogen replacement to ensure that the air in the reaction kettle is completely replaced; and then, switching to hydrogen replacement for 3-5 times, and continuously introducing hydrogen for replacement for about 5-10 min to ensure that the nitrogen in the reaction kettle is replaced thoroughly. After the replacement is finished, the pressure in the kettle is increased to 4.5MPa, the rotating speed is controlled to be 1000rpm/min, then the reaction temperature is increased to 85 ℃, the hydrogenation is carried out by adopting a variable-temperature continuous hydrogen-introduction constant-pressure mode, and the temperature of the material discharged from the kettle is controlled to be 70 ℃. And (3) after the hydrogenation solution is taken out, firstly, carrying out negative pressure filtration, recovering the catalyst for next cycle use, and carrying out reducing sugar content analysis after the volume of the hydrogenation filtrate is determined to 1L after the hydrogenation filtrate is recovered.
Example 12
10g (dry basis) of the self-prepared ruthenium on carbon catalyst were weighed. Preparing a 40-50% glucose solution, wherein the total amount of the glucose solution is 400g, (m)(catalyst)：m(sugar solution)＝1：40)。
Firstly, adding 10g of ruthenium-carbon catalyst (Ru/AC) with 1% loading capacity into a high-pressure hydrogenation reaction kettle with an effective volume of 1L, then adding a dissolved glucose solution into the reaction kettle, sealing the reaction kettle, firstly performing nitrogen replacement for 3-5 times, and then continuously introducing nitrogen for about 5-10 min for nitrogen replacement to ensure that the air in the reaction kettle is completely replaced; and then, switching to hydrogen replacement for 3-5 times, and continuously introducing hydrogen for replacement for about 5-10 min to ensure that the nitrogen in the reaction kettle is replaced thoroughly. After the replacement is finished, the pressure in the kettle is increased to 4MPa, the rotating speed is controlled at 1000rpm/min, then the reaction temperature is increased to 85 ℃, the hydrogenation is carried out by adopting a variable-temperature continuous hydrogen-introduction constant-pressure mode, and the temperature of the material discharged from the kettle is controlled at 100 ℃. And (3) after the hydrogenation solution is taken out, firstly, carrying out negative pressure filtration, recovering the catalyst for next cycle use, and carrying out reducing sugar content analysis after the volume of the hydrogenation filtrate is determined to 1L after the hydrogenation filtrate is recovered.
Comparative example 1
A total of 400g of a 50% glucose solution was prepared.
Firstly, adding a dissolved glucose solution into a high-pressure hydrogenation reaction kettle with an effective volume of 1L, then closing the reaction kettle, and then carrying out air replacement in the kettle. Firstly, performing nitrogen replacement for 3-5 times, and then continuously introducing nitrogen for about 5-10 min for replacement so as to ensure thorough replacement of air in the reaction kettle; and then, switching to hydrogen replacement for 3-5 times, and continuously introducing hydrogen for replacement for about 5-10 min to ensure that the nitrogen in the reaction kettle is replaced thoroughly. After the replacement is finished, the pressure in the kettle is increased to 4MPa, the rotating speed is controlled at 1000rpm/min, then the reaction temperature is increased to 85 ℃, the hydrogenation is carried out by adopting a variable-temperature continuous hydrogen-introduction constant-pressure mode, and the temperature of the material discharged from the kettle is controlled at 100 ℃. And (3) after the hydrogenation solution is taken out, firstly, carrying out negative pressure filtration, recovering the catalyst for next cycle use, and carrying out reducing sugar content analysis after the volume of the hydrogenation filtrate is determined to 1L after the hydrogenation filtrate is recovered.
Comparative example 2
10g (dry basis) of the self-prepared ruthenium on carbon catalyst were weighed. Preparing a 50% glucose solution, 400g (m)(catalyst)：m(sugar solution)＝1：40)。
Firstly, adding 10g of ruthenium-carbon catalyst (Ru/AC) with 1% loading capacity into a high-pressure hydrogenation reaction kettle with an effective volume of 1L, then adding a dissolved glucose solution into the reaction kettle, sealing the reaction kettle, firstly performing nitrogen replacement for 3-5 times, and then continuously introducing nitrogen for about 5-10 min for nitrogen replacement to ensure that the air in the reaction kettle is completely replaced; and then, switching to hydrogen replacement for 3-5 times, and continuously introducing hydrogen for replacement for about 5-10 min to ensure that the nitrogen in the reaction kettle is replaced thoroughly. After the replacement is finished, the pressure in the kettle is increased to 4MPa, the rotating speed is controlled at 1000rpm/min, then the reaction temperature is increased to 85 ℃, the hydrogenation is carried out by adopting a variable-temperature continuous hydrogen-introduction constant-pressure mode, and the temperature of the material discharged from the kettle is controlled at 120 ℃. And (3) after the hydrogenation solution is taken out, firstly, carrying out negative pressure filtration, recovering the catalyst for next cycle use, and carrying out reducing sugar content analysis after the volume of the hydrogenation filtrate is determined to 1L after the hydrogenation filtrate is recovered.
Comparative example 3
10g (dry basis) of the self-prepared ruthenium on carbon catalyst were weighed. Preparing a 50% glucose solution, 400g (m)(catalyst)：m(sugar solution)＝1：40)。
Firstly, adding 10g of ruthenium-carbon catalyst (Ru/AC) with 1% loading capacity into a high-pressure hydrogenation reaction kettle with an effective volume of 1L, then adding a dissolved glucose solution into the reaction kettle, sealing the reaction kettle, firstly performing nitrogen replacement for 3-5 times, and then continuously introducing nitrogen for about 5-10 min for nitrogen replacement to ensure that the air in the reaction kettle is completely replaced; and then, switching to hydrogen replacement for 3-5 times, and continuously introducing hydrogen for replacement for about 5-10 min to ensure that the nitrogen in the reaction kettle is replaced thoroughly. After the replacement is finished, the pressure in the kettle is increased to 4MPa, the rotating speed is controlled at 1000rpm/min, then the reaction temperature is increased to 85 ℃, the hydrogenation is carried out by adopting a variable-temperature continuous hydrogen-introduction constant-pressure mode, and the temperature of the material discharged from the kettle is controlled at 110 ℃. And (3) after the hydrogenation solution is taken out, firstly, carrying out negative pressure filtration, recovering the catalyst for next cycle use, and carrying out reducing sugar content analysis after the volume of the hydrogenation filtrate is determined to 1L after the hydrogenation filtrate is recovered.
Comparative example 4
10g (dry basis) of the self-prepared ruthenium on carbon catalyst were weighed. A50% glucose solution was prepared in an amount of 400g in total, and the pH of the sugar solution was adjusted to 7.5.
Firstly, adding 10g of ruthenium-carbon catalyst (Ru/AC) with 1% loading capacity into a high-pressure hydrogenation reaction kettle with an effective volume of 1L, then adding a dissolved glucose solution into the reaction kettle, sealing the reaction kettle, firstly performing nitrogen replacement for 3-5 times, and then continuously introducing nitrogen for about 5-10 min for nitrogen replacement to ensure that the air in the reaction kettle is completely replaced; and then, switching to hydrogen replacement for 3-5 times, and continuously introducing hydrogen for replacement for about 5-10 min to ensure that the nitrogen in the reaction kettle is replaced thoroughly. After the replacement is finished, the pressure in the kettle is increased to 4MPa, the rotating speed is controlled at 1000rpm/min, then the reaction temperature is increased to 120 ℃, the constant-temperature continuous hydrogen-introduction constant-pressure mode is adopted for hydrogenation, and the kettle outlet temperature is controlled at 70 ℃. And (3) after the hydrogenation solution is taken out, firstly, carrying out negative pressure filtration, recovering the catalyst for next cycle use, and carrying out reducing sugar content analysis after the volume of the hydrogenation filtrate is determined to 1L after the hydrogenation filtrate is recovered.
The glucose hydrogenation process route was evaluated for each of the examples and comparative examples, and the evaluation results are shown in table 1.
TABLE 1 comparison of glucose hydroconversion Performance
| Examples | Glucose conversion (%) | Examples | Glucose conversion (%) |
| Example 2 | 70.60 | Example 10 | 90.73 |
| Example 3 | 96.31 | Example 11 | 100 |
| Example 4 | 96.08 | Example 12 | 100 (sorbitol Selectivity 100) |
| Example 5 | 96.33 | Comparative example 1 | 0 |
| Example 6 | 95.71 | Comparative example 2 | 77.41 |
| Example 7 | 73.15 | Comparative example 3 | 85.74 |
| Example 8 | 93.46 | Comparative example 4 | 100 |
| Example 9 | 89.37 |
It can be seen from table 1 that the novel controlled hydrogenation mode, optimized process parameters and self-prepared ruthenium/carbon catalyst of the present invention can achieve very high conversion rate for catalytic glucose hydrogenation, the conversion rate of glucose can reach 100%, and the selectivity can also reach 100% by high performance liquid chromatography. Comparative example 1 is the case without catalyst, where no reaction occurs and the conversion is 0; in comparative examples 2 and 3, the temperature of the material discharged from the reaction kettle is different, and the higher the temperature is, the better the material is discharged, and the higher the temperature is, the material is possibly not completely converted; in comparative example 4, although 100% conversion of glucose was achieved, the pH of the sugar solution was adjusted, a constant temperature heating method was used, the temperature of the discharged material in the reaction vessel was low, and the temperature change method and the high temperature discharging method were not used to save time and cost in terms of economic applicability (operation time, labor intensity, and cost).
Achieves high conversion rate of glucose and provides a solid theoretical basis for preparing sorbitol by hydrogenation in an industrial batch reaction kettle. Through repeated cycle measurement, the process route, the control method and the self-made catalyst can achieve good practical effect. Compared with the prior art, the method has the main advantages of low self-made catalyst loading rate, small Ru nano-particles, high reaction activity, milder reaction conditions, no need of adjusting the pH value of the sugar solution, great improvement on the operation safety and effective reduction of the production cost.
Claims (9)
1. A method for preparing sugar alcohol by catalytic hydrogenation is characterized by comprising the following steps:
(1) firstly, dissolving glucose at 50-60 ℃, wherein the mass concentration is 40-55%, and the total mass is 400 g;
(2) adding a ruthenium-carbon catalyst into a high-pressure hydrogenation reaction kettle with an effective volume of 1L, and then adding the sugar liquid obtained in the step (1), wherein the mass ratio of the added amount of the ruthenium-carbon catalyst to the dry sugar is preferably 4-6.5%;
(3) firstly introducing N into a sealed reaction kettle2Replacing air in the kettle for 3-5 times, and then continuously introducing N2Completely replacing the air in the kettle for 5-10 min;
(4) switching gas source to H2Then, H is introduced first2Replacing air in the kettle for 3-5 times, and then continuously introducing H25-10 min to completely replace N in the kettle2；
(5) Raising the stirring speed to 700-1200 rpm/min, then raising the temperature to 80-130 ℃, controlling the pressure to be raised to 2.5-4.5 MPa, turning off the heating power supply when the temperature reaches a set value, and continuously introducing H at the moment2Maintaining a constant voltage mode;
(6) when the reaction is finished, controlling the temperature of the reaction materials discharged from the kettle to be 50-120 ℃;
(7) and (3) taking out the hydrogenation solution, carrying out negative pressure filtration, recovering the catalyst for next cycle use, recovering the hydrogenation filtrate to a certain volume, and carrying out a reducing sugar titration test and High Performance Liquid Chromatography (HPLC) analysis.
2. The method for preparing sugar alcohol by catalytic hydrogenation according to claim 1, wherein: the mass concentration of the glucose solution in the step (1) is 50%.
3. The method for preparing sugar alcohol by catalytic hydrogenation according to claim 2, wherein: the mass ratio of the added mass of the ruthenium-carbon catalyst in the step (2) to the glucose solution is 1: 40.
4. a process for the preparation of sugar alcohols by catalytic hydrogenation according to claim 1, 2 or 3, characterized in that: the ruthenium carbon catalyst in the step (2) is prepared by the following steps:
1) weighing 200-300 meshes, and the specific surface area is 1000-2000 m2Adding the powder active carbon per gram into a three-neck flask or a beaker; adding ultrapure water into activated carbon, wherein the volume weight ratio of the ultrapure water to the activated carbon is V(Water)：m(activated carbon)Stirring at a low speed of 2-14, adding a ruthenium-containing Ru precursor compound into the carbon slurry solution, adjusting the pH value of the solution to obtain a dipping mixed solution of the ruthenium-containing carbon solution,
2) dipping the dipping mixed solution containing the ruthenium-carbon solution for 45 min-3 h, and then adjusting the pH value of the dipping mixed solution to 10-11 again;
3) adding a reducing agent, wherein the molar ratio of the reducing agent to Ru atoms is 1: 1, preparing a solution with the same volume as the impregnation mixed solution, adding the solution into the step (2), and rapidly increasing the stirring speed to 450-500 rpm/min, wherein the reduction time is 1-2 h, and the reduction temperature is 10-30 ℃;
4) after reduction, removing the impregnation liquid by adopting a positive pressure filtration mode, then washing the catalyst solid powder to be neutral by adopting ultrapure water, obtaining the ruthenium-carbon catalyst after filtration, and sealing and storing at room temperature for later use, wherein the electric conductivity is less than 20 mu s/cm.
5. The method for preparing sugar alcohol by catalytic hydrogenation according to claim 4, wherein: the mass percentage of the ruthenium is 0.5-5%.
6. The method for preparing sugar alcohol by catalytic hydrogenation according to claim 4, wherein: the precursor compound containing ruthenium Ru in the step 1) is chlorine-containing ruthenium salt.
7. The method for preparing sugar alcohol by catalytic hydrogenation according to claim 4, wherein: the pH value of the dipping mixed solution of the ruthenium-containing carbon solution in the step 1) is 0.8-7.
8. The method for preparing sugar alcohol by catalytic hydrogenation according to claim 4, wherein: the dipping temperature of the dipping mixed solution of the ruthenium-containing carbon solution in the step 2) is 10-30 ℃.
9. The method for preparing sugar alcohol by catalytic hydrogenation according to claim 4, wherein: the reducing agent in the step 3) adopts methanol, ethanol, glycol, ascorbic acid AA, potassium borohydride KBH4Or sodium borohydride.
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Application publication date: 20210810 |