CN111167445A - Supported Ru-based catalyst and preparation method and application thereof - Google Patents
Supported Ru-based catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN111167445A CN111167445A CN202010142431.7A CN202010142431A CN111167445A CN 111167445 A CN111167445 A CN 111167445A CN 202010142431 A CN202010142431 A CN 202010142431A CN 111167445 A CN111167445 A CN 111167445A
- Authority
- CN
- China
- Prior art keywords
- supported
- based catalyst
- solution
- cellulose
- microspheres
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000001913 cellulose Substances 0.000 claims abstract description 62
- 229920002678 cellulose Polymers 0.000 claims abstract description 62
- 239000004005 microsphere Substances 0.000 claims abstract description 61
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 39
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 14
- 239000004202 carbamide Substances 0.000 claims description 14
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 13
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical group CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 13
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 13
- 239000005457 ice water Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 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 claims description 12
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000000600 sorbitol Substances 0.000 claims description 12
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 11
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 10
- 239000008103 glucose Substances 0.000 claims description 10
- 150000003303 ruthenium Chemical class 0.000 claims description 9
- 239000012670 alkaline solution Substances 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims description 8
- 238000006722 reduction reaction Methods 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 8
- 239000003995 emulsifying agent Substances 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 229910021603 Ruthenium iodide Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 12
- 229960001031 glucose Drugs 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910019891 RuCl3 Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229930006000 Sucrose Natural products 0.000 description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 229960004793 sucrose Drugs 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- -1 ruthenium ions Chemical class 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229930003268 Vitamin C Natural products 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 235000015895 biscuits Nutrition 0.000 description 1
- 235000012970 cakes Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000003933 environmental pollution control Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 235000015243 ice cream Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 235000015067 sauces Nutrition 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a supported Ru-based catalyst and a preparation method and application thereof, and relates to the technical field of catalysts. The supported Ru-based catalyst comprises a cellulose microsphere and Ru loaded on the cellulose microsphere, wherein the Ru accounts for 3% -10% of the mass of the cellulose microsphere. The cellulose microsphere is rich in heavy metal adsorption active functional groups and adsorption sites, is easy to biodegrade and has no pollution to the environment, and the activity of the catalyst is effectively improved by taking the cellulose microsphere as a carrier. Therefore, compared with the existing Ru-based catalyst, the supported Ru-based catalyst prepared by the invention has the advantages of low cost, environmental protection and higher catalytic activity.
Description
Technical Field
The invention relates to the technical field of catalysts, and particularly relates to a supported Ru-based catalyst, and a preparation method and application thereof.
Background
Sorbitol, alternative name sorbitol, formula C6H14O6Molecular weight 182.17, is white hygroscopic powder or crystalline powder, tablet or granule, and is odorless. Depending on the crystallization conditions, the melting point varies from 88 to 102 ℃, the relative density is about 1.49, the sugar-free sucrose-containing syrup is easily soluble in water (1g is dissolved in about 0.45mL of water), slightly soluble in ethanol and acetic acid, has cool sweetness which is about 0.7 times of that of sucrose,the calorific value is similar to that of cane sugar. Sorbitol has sugar alcohol commonality of low sugar content, low calorific value, no decayed tooth and the like, and unique moisture retention, stability and crystallization resistance, and is widely applied to the food fields of various candies, cakes, biscuits, ice creams, jellies, beverages, sauces and the like. In the pharmaceutical chemical field, the surfactant can also be used as a raw material for producing vitamin C, span and Tween surfactants, has wide application, and is an important product related to industrial development and national civilian life.
Currently, in industrial production, sorbitol is mainly prepared by catalyzing glucose hydrogenation reaction by a metal catalyst. In early research, metallic nickel is mainly used as an active metal, but a catalyst prepared from the metal has poor stability, is easy to run off in the reaction process, and has high raw material cost and great pollution. In view of the technical deficiency, great attention is paid to how to obtain a catalyst with high catalytic performance and good stability. With the progress of research, currently, sorbitol is mainly produced by a Ru/C catalyst which can recover noble metal Ru by incineration, acid dissolution or the like, but CO is caused by consumption of activated carbon, inorganic acid or the like2And the discharge of waste acid, such conventional recovery processes of metallic Ru are not environmentally friendly.
Disclosure of Invention
The invention mainly aims to provide a supported Ru-based catalyst, a preparation method and application thereof, and aims to provide a novel supported catalyst for hydrogenation.
In order to achieve the purpose, the invention provides a supported Ru-based catalyst, which comprises cellulose microspheres and Ru loaded on the cellulose microspheres, wherein the loading amount of the Ru in the supported Ru-based catalyst is 3% -10%.
In order to achieve the above object, the present invention also provides a preparation method of the supported Ru-based catalyst, comprising the steps of:
s10, dissolving the cellulose linter pulp in an alkaline solution, centrifuging and defoaming to prepare a cellulose solution, adding epichlorohydrin in an ice water bath, and uniformly mixing to prepare a mixed solution;
s20, stirring and uniformly mixing the emulsifier and the isooctane in an ice-water bath, adding the mixed solution, continuously stirring to form microspheres, removing the solvent on the surfaces of the microspheres, and freeze-drying the microspheres to obtain cellulose microspheres;
s30, adding the cellulose microspheres into a water solution of water-soluble ruthenium salt, stirring to form a reaction solution, and then carrying out high-temperature reduction reaction for 1-4 hours in an argon flow at the temperature of 250-800 ℃ to obtain the supported Ru-based catalyst.
Alternatively, in step S10, the alkaline solution is any one of an aqueous solution of a mixture of LiOH and urea, an aqueous solution of a mixture of NaOH and urea, and an aqueous solution of a mixture of NaOH and thiourea.
Alternatively, in step S10, the conditions for centrifugal defoaming are: the temperature is 0-5 ℃, and the rotating speed is 6000-80000 rpm.
Optionally, in step S10, the volume ratio of the epichlorohydrin to the cellulose solution is (1-3): 100.
optionally, in step S20, the emulsifier is Span 80, wherein the ratio of the mass of Span 80 to the volume of isooctane is (40-60) g: 300 mL.
Optionally, in step S20, the volume ratio of the mixed solution to isooctane is 1 (4-6).
Alternatively, in step S30, the aqueous solution of the water-soluble ruthenium salt is RuCl3Solution, RuI3Solution, C6H9O6Any one of Ru solutions.
Alternatively, in step S30, the mass ratio of the ruthenium content in the aqueous solution of the water-soluble ruthenium salt to the cellulose microspheres is 0.006: (0.03-0.05).
Furthermore, the invention also provides a method for synthesizing sorbitol by glucose hydrogenation, wherein the hydrogenation catalyst used in the reaction is a supported Ru-based catalyst, and the supported Ru-based catalyst is the supported Ru-based catalyst.
In the technical scheme provided by the invention, the supported Ru-based catalyst is prepared by taking cellulose microspheres as a carrier and loading metal ruthenium. The cellulose microsphere is rich in heavy metal adsorption active functional groups and adsorption sites, is easy to biodegrade, has no pollution to the environment, can uniformly adsorb more Ru by taking the cellulose microsphere as a carrier, and effectively improves the activity of the catalyst. Therefore, compared with the existing Ru-based catalyst, the supported Ru-based catalyst prepared by the invention has the advantages of low cost, environmental protection and higher catalytic activity.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments.
It should be noted that those whose specific conditions are not specified in the examples were performed according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. In addition, the meaning of "and/or" appearing throughout includes three juxtapositions, exemplified by "A and/or B" including either A or B or both A and B. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the existing process of preparing sorbitol by glucose hydrogenation, the used metal catalysts have certain defects, some catalysts have poor stability, and some catalysts are not beneficial to recovery and pollute the environment.
In view of this, the invention provides a supported Ru-based catalyst, and aims to provide a novel supported catalyst for hydrogenation, which is low in cost, environment-friendly and higher in catalytic activity. The supported Ru-based catalyst comprises cellulose microspheres and Ru loaded on the cellulose microspheres, wherein the loading amount of the Ru in the supported Ru-based catalyst is 3% -10%. Ru is ruthenium metal.
The active carbon has the characteristics of developed pore structure, large specific surface area, easy chemical modification and excellent adsorption performance, and is widely applied to impurity removal, decolorization and environmental pollution control in food and pharmaceutical industries, industrial catalyst carriers and the like. Cellulose is a main component of plant cell walls, is a product of photosynthesis, and is a biomass resource with the most abundant reserves in the nature, wherein the cellulose in the straws of grain crops accounts for about 40 percent. The cellulose is used as the raw material of the activated carbon carrier, so that natural resources are fully utilized, and a new way for utilizing the cellulose is developed.
In the technical scheme provided by the invention, the supported Ru-based catalyst is prepared by taking cellulose microspheres as a carrier and loading metal ruthenium. The cellulose microsphere is rich in heavy metal adsorption active functional groups and adsorption sites, is easy to biodegrade, has no pollution to the environment, can uniformly adsorb more Ru by taking the cellulose microsphere as a carrier, and effectively improves the activity of the catalyst. Therefore, compared with the existing Ru-based catalyst, the supported Ru-based catalyst prepared by the invention has the advantages of low cost, environmental protection and higher catalytic activity.
Based on the supported Ru-based catalyst, the invention also provides a preparation method of the supported Ru-based catalyst, which comprises the following steps:
and step S10, dissolving the cellulose linter pulp in an alkaline solution, performing centrifugal deaeration to prepare a cellulose solution, adding epoxy chloropropane in an ice-water bath, and uniformly mixing to prepare a mixed solution.
The cellulose linter pulp is used as a raw material to prepare the cellulose microspheres, is a main component of cotton, is a renewable biomass resource, has wide source, low price, quick degradation and little environmental pollution.
In one embodiment, the mass ratio of the cellulose linter pulp to the alkaline solution is (4-6): 100. in order to ensure good dissolving effect, the temperature of the alkaline solution is-11 ℃ to-13 ℃, and the alkaline solution is any one of an aqueous solution of a mixture of LiOH and urea, an aqueous solution of a mixture of NaOH and urea and an aqueous solution of a mixture of NaOH and thiourea. Further, the mass percentages of LiOH and urea in the aqueous solution of the mixture of LiOH and urea are respectively 4-5% and 14-16%, the mass percentages of NaOH and urea in the aqueous solution of the mixture of NaOH and urea are respectively 6-7% and 11-12%, and the mass percentages of NaOH and thiourea in the aqueous solution of the mixture of NaOH and thiourea are respectively 9-10% and 4-5%. Preferably, the conditions for the centrifugal defoaming are as follows: the temperature is 0-5 ℃, and the rotating speed is 6000-80000 rpm. In addition, the volume ratio of the epichlorohydrin to the cellulose solution is (1-3): 100.
and step S20, stirring and uniformly mixing the emulsifier and the isooctane in an ice-water bath, adding the mixed solution, continuously stirring to form microspheres, removing the solvent on the surfaces of the microspheres, and freeze-drying the microspheres to obtain the cellulose microspheres.
Wherein the emulsifier is Span 80, and the volume ratio of the mass of the Span 80 to the isooctane is (40-60) g: 300 mL. Furthermore, the volume ratio of the mixed solution to the isooctane is 1 (4-6). In this embodiment, the implementation is as follows: stirring and uniformly mixing Span 80 and isooctane in an ice-water bath, adding the mixed solution while stirring for 0.5-1 h, removing the water bath, continuously stirring for 2-3 h to form microspheres, removing the solvent on the surfaces of the microspheres by using ethanol and ionized water, and freeze-drying the microspheres to obtain the cellulose microspheres.
Step S30, adding the cellulose microspheres into a water solution of water-soluble ruthenium salt, stirring to form a reaction solution, and then carrying out high-temperature reduction reaction for 1-4 h in an argon flow at the temperature of 250-800 ℃ to obtain the supported Ru-based catalyst.
The water solution of the water-soluble ruthenium salt is RuCl3Solution, RuI3Solution, C6H9O6Any one of Ru solutions. Further, the mass ratio of the ruthenium content in the water solution of the water-soluble ruthenium salt to the cellulose microspheres is 0.006: (0.03-0.05). To prevent agglomeration of Ru on the cellulose microspheres, a high temperature reduction reaction is carried out in a stream of argon, which provides a very good inert atmosphere in which to formIn the atmosphere, the hydroxyl on the surface of the cellulose microsphere can directly reduce ruthenium ions adsorbed on the surface of the cellulose microsphere, and the hydroxyl on the surface of the cellulose microsphere and the adsorbed ruthenium ions are uniformly distributed on the surface of the cellulose microsphere, so that the reduction is more uniform by adopting the method, the active sites of the cellulose microsphere serving as a carrier are enriched, and the catalytic activity of the prepared supported Ru-based catalyst is improved.
The invention further provides an application of the supported Ru-based catalyst, and the supported Ru-based catalyst can be used in the reaction of synthesizing sorbitol by hydrogenating glucose.
The technical solutions of the present invention are further described in detail with reference to the following specific examples, which should be understood as merely illustrative and not limitative.
Example 1
(1) 5g of cellulose linter pulp was dissolved in 100g of an aqueous LiOH/urea solution (LiOH/urea mass ratio 4:15) precooled to-12 ℃ and centrifuged and defoamed at 3 ℃ at 7000 rpm. Under the condition of ice-water bath, 2mL of epichlorohydrin is added into 100mL of cellulose solution and stirred to ensure that the epichlorohydrin is uniformly dispersed, so as to obtain a mixed solution. Meanwhile, under the ice-water bath, 40g of Span-80 and 300mL of isooctane are added into a 500mL three-neck flask and stirred to ensure that the Span-80 is uniformly dispersed. Then, 75mL of the mixed solution was added with stirring and stirred for 45min, and the ice bath was removed and stirring was continued for 2.5h to obtain microspheres. And (3) cleaning the solvent on the surface of the microsphere by using ethanol and deionized water, and freeze-drying the microsphere to obtain the cellulose microsphere.
(2) 0.04g of cellulose microspheres are added into 4.7ml of 3.5504g/L RuCl3Stirring the solution to form a reaction solution, and then carrying out high-temperature reduction reaction for 2 hours in argon flow at the temperature of 250 ℃ to prepare the supported Ru-based catalyst.
Example 2
(1) 4g of cellulose linter pulp was dissolved in 100g of NaOH/urea aqueous solution (NaOH/urea mass ratio 6:11) precooled to-11 ℃ and centrifuged and defoamed at 0 ℃ at 6000 rpm. Under the condition of ice-water bath, 1mL of epichlorohydrin is added into 100mL of cellulose solution and stirred to ensure that the epichlorohydrin is uniformly dispersed, so as to obtain a mixed solution. Meanwhile, under an ice-water bath, 50g of Span-80 and 300mL of isooctane were added to a 500mL three-necked flask, and stirred to disperse the Span-80 uniformly. Then, 60mL of the mixed solution was added with stirring and stirred for 1h, and the ice bath was removed and stirring was continued for 3h to obtain microspheres. And (3) cleaning the solvent on the surface of the microsphere by using ethanol and deionized water, and freeze-drying the microsphere to obtain the cellulose microsphere.
(2) 0.03g of cellulose microspheres are added to 4.7ml of 3.5504g/L RuCl3Stirring the solution to form a reaction solution, and then carrying out high-temperature reduction reaction for 2 hours in argon flow at 500 ℃ to prepare the supported Ru-based catalyst.
Example 3
(1) 6g of cellulose linter pulp was dissolved in 100g of an aqueous NaOH/thiourea solution (NaOH/thiourea mass ratio 9:4) precooled to-13 ℃ and centrifuged and defoamed at 5 ℃ at 8000 rpm. Under the ice-water bath, 3mL of epichlorohydrin is added into 100mL of cellulose solution and stirred to uniformly disperse the epichlorohydrin, so as to obtain a mixed solution. Meanwhile, under the ice-water bath, 60g of Span-80 and 300mL of isooctane are added into a 500mL three-neck flask and stirred to ensure that the Span-80 is uniformly dispersed. Then, 50mL of the mixed solution was added with stirring and stirred for 30min, and the ice bath was removed and stirring was continued for 2h to obtain microspheres. And (3) cleaning the solvent on the surface of the microsphere by using ethanol and deionized water, and freeze-drying the microsphere to obtain the cellulose microsphere.
(2) 0.05g of cellulose microspheres are added to 4.7ml of 3.5504g/L RuCl3Stirring the solution to form a reaction solution, and then carrying out high-temperature reduction reaction for 2 hours in argon flow at 800 ℃ to prepare the supported Ru-based catalyst.
The conversion rate of glucose in the reaction of hydrogenating glucose to prepare sorbitol in each catalyst was tested using commercially available Ru/C catalyst (national pharmaceutical products chemical Co., Ltd., CAS: 7440-18-8) as a comparative example and the supported Ru-based catalysts prepared in examples 1-3 as an experimental group, and the methods and results were as follows:
weighing 0.18g of anhydrous glucose powder, adding 2mL of deionized water to dissolve the anhydrous glucose powder, placing the anhydrous glucose powder in a reaction kettle, heating the mixture to 120 ℃ in a hydrogen atmosphere, adding 0.01g of the cellulose-based ruthenium catalyst, adjusting the pressure in the kettle to 4MPa, reacting for 30min, sampling, and analyzing the concentration of sorbitol in a sample by adopting a high performance liquid chromatography, wherein the results are shown in Table 1.
TABLE 1 post-reaction glucose conversion
| Catalyst and process for preparing same | Glucose conversion (%) |
| Example 1 | 90 |
| Example 2 | 95 |
| Example 3 | 99 |
| Ru/C catalyst | 84 |
The results in table 1 show that the supported Ru-based catalyst prepared by the invention has better catalytic effect than the existing Ru/C catalyst in the reaction of synthesizing sorbitol by hydrogenating glucose. Meanwhile, the larger the dosage of the emulsifier is, the higher the temperature of argon flow is, and the better the catalytic reaction activity of the supported Ru-based catalyst is improved.
The above is only a preferred embodiment of the present invention, and it is not intended to limit the scope of the invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall be included in the scope of the present invention.
Claims (10)
1. The supported Ru-based catalyst is characterized by comprising cellulose microspheres and Ru loaded on the cellulose microspheres, wherein the loading amount of the Ru in the supported Ru-based catalyst is 3% -10%.
2. A process for the preparation of a supported Ru-based catalyst according to claim 1, comprising the steps of:
s10, dissolving the cellulose linter pulp in an alkaline solution, centrifuging and defoaming to prepare a cellulose solution, adding epichlorohydrin in an ice water bath, and uniformly mixing to prepare a mixed solution;
s20, stirring and uniformly mixing the emulsifier and the isooctane in an ice-water bath, adding the mixed solution, continuously stirring to form microspheres, removing the solvent on the surfaces of the microspheres, and freeze-drying the microspheres to obtain cellulose microspheres;
s30, adding the cellulose microspheres into a water solution of water-soluble ruthenium salt, stirring to form a reaction solution, and then carrying out high-temperature reduction reaction for 1-4 hours in an argon flow at the temperature of 250-800 ℃ to obtain the supported Ru-based catalyst.
3. The method of preparing the supported Ru-based catalyst according to claim 2, wherein the alkaline solution is any one of an aqueous solution of a mixture of LiOH and urea, an aqueous solution of a mixture of NaOH and urea, and an aqueous solution of a mixture of NaOH and thiourea in step S10.
4. The method for producing a supported Ru-based catalyst according to claim 2, wherein in step S10, the conditions for the centrifugal defoaming are: the temperature is 0-5 ℃, and the rotating speed is 6000-80000 rpm.
5. The method for preparing the supported Ru-based catalyst according to claim 2, wherein in step S10, the volume ratio of the epichlorohydrin to the cellulose solution is (1 to 3): 100.
6. the method for preparing the supported Ru-based catalyst according to claim 2, wherein in step S20, the emulsifier is Span 80, and a volume ratio of a mass of the Span 80 to isooctane is (40-60) g: 300 mL.
7. The method for preparing the supported Ru-based catalyst according to claim 2, wherein in step S20, the volume ratio of the mixed solution to isooctane is 1 (4-6).
8. The method for preparing a supported Ru-based catalyst according to claim 2, wherein the aqueous solution of water-soluble ruthenium salt is RuCl in step S303Solution, RuI3Solution, C6H9O6Any one of Ru solutions.
9. The method of preparing a supported Ru-based catalyst according to claim 2, wherein in step S30, the mass ratio of the ruthenium content in the aqueous solution of the water-soluble ruthenium salt to the cellulose microspheres is 0.006: (0.03-0.05).
10. A method for synthesizing sorbitol by glucose hydrogenation is characterized in that a hydrogenation catalyst used in the reaction is a supported Ru-based catalyst, and the supported Ru-based catalyst is the supported Ru-based catalyst according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010142431.7A CN111167445A (en) | 2020-03-03 | 2020-03-03 | Supported Ru-based catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010142431.7A CN111167445A (en) | 2020-03-03 | 2020-03-03 | Supported Ru-based catalyst and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111167445A true CN111167445A (en) | 2020-05-19 |
Family
ID=70649642
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010142431.7A Pending CN111167445A (en) | 2020-03-03 | 2020-03-03 | Supported Ru-based catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111167445A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109569591A (en) * | 2018-12-19 | 2019-04-05 | 武汉轻工大学 | A kind of cellulose base Ru/C catalyst and preparation method thereof |
-
2020
- 2020-03-03 CN CN202010142431.7A patent/CN111167445A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109569591A (en) * | 2018-12-19 | 2019-04-05 | 武汉轻工大学 | A kind of cellulose base Ru/C catalyst and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| XIAODONG WU ET AL: ""A novel reagentless approach for synthesizing cellulose nanocrystal-supported palladium nanoparticles with enhanced catalytic performance"", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| 吴俊杰: ""天然纤维素复合功能材料的结构调控及性质研究"", 《中国优秀硕士论文全文数据库》 * |
| 高晓月等: ""纤维素制备碳材料的工艺与机理研究"", 《化工新型材料》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101012387B (en) | Technique for manufacturing liquid fuel from highly effective cellulose biomass | |
| CN101778955B (en) | Method for saccharification and separation of plant fiber material | |
| CN102533717B (en) | Method for immobilizing beta-glucosidase and hydrolyzing straw cellulose by cooperating beta-glucosidase with cellulase | |
| Huwig et al. | Laboratory procedures for producing 2-keto-D-glucose, 2-keto-D-xylose and 5-keto-D-fructose from D-glucose, D-xylose and L-sorbose with immobilized pyranose oxidase of Peniophora gigantea | |
| CN110270366A (en) | It is a kind of for being catalyzed the preparation method of glucose isomerization high activated catalyst | |
| CN103484512A (en) | Method for producing high-functional-trisaccharide-content isomaltooligosaccharide by using immobilized cells | |
| JP2010094093A (en) | Method for producing ethanol from hull of citrus | |
| CN111167445A (en) | Supported Ru-based catalyst and preparation method and application thereof | |
| CN110368977B (en) | Preparation method and application of calcium-magnesium double-active-center catalyst | |
| EP3418269B1 (en) | Method for producing sugar alcohol | |
| CN100582228C (en) | Immobilization lipase, and preparation method | |
| CN111440834A (en) | Preparation method of low-viscosity high-maltotetraose-content oligomeric maltose syrup | |
| CN106867990B (en) | Preparation method of immobilized beta-glucosidase | |
| CN111167444A (en) | Supported Pd-based catalyst and preparation method and application thereof | |
| CN106047963A (en) | Method for producing high fructose syrup by immobilized glucose isomerase | |
| EP4317429A1 (en) | Method for producing tagatose by immobilized multi-enzyme system | |
| CN102617752A (en) | Production process of low molecular weight pectin | |
| CN109369731A (en) | A kind of method of glucose during removing xylose production | |
| CN101182563B (en) | Method for preparing lactulose by co-immobilized lactose enzyme and glucose isomerase | |
| CN101792780B (en) | Separation method of D-glucuronic acid gamma-lactone | |
| JP3513197B2 (en) | Method for producing high purity maltitol | |
| CN113185394A (en) | Method for preparing levulinic acid by using Dowson configuration tungsten-phosphorus heteropoly acid for catalyzing and hydrolyzing cellulose | |
| CN113582174A (en) | Preparation method of straw activated carbon, straw activated carbon and application | |
| CN100999741A (en) | Process of extracting mannitol using glucose mother liquid | |
| Mishra et al. | Immobilization of Penicillium funiculosum cellulase on a soluble polymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200519 |
|
| RJ01 | Rejection of invention patent application after publication |