CN116618058A - Catalyst, preparation method thereof and method for preparing lactic acid by catalysis of saccharides - Google Patents
Catalyst, preparation method thereof and method for preparing lactic acid by catalysis of saccharides Download PDFInfo
- Publication number
- CN116618058A CN116618058A CN202310496566.7A CN202310496566A CN116618058A CN 116618058 A CN116618058 A CN 116618058A CN 202310496566 A CN202310496566 A CN 202310496566A CN 116618058 A CN116618058 A CN 116618058A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- lactic acid
- reaction
- biomass
- siliceous
- 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
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 235000014655 lactic acid Nutrition 0.000 title claims abstract description 50
- 239000004310 lactic acid Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 30
- 150000001720 carbohydrates Chemical class 0.000 title claims abstract description 28
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 239000002028 Biomass Substances 0.000 claims abstract description 41
- 238000011068 loading method Methods 0.000 claims abstract description 15
- 229910020646 Co-Sn Inorganic materials 0.000 claims abstract description 13
- 229910020709 Co—Sn Inorganic materials 0.000 claims abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000001913 cellulose Substances 0.000 claims description 24
- 229920002678 cellulose Polymers 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 10
- 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 9
- 239000008103 glucose Substances 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 230000001681 protective effect Effects 0.000 claims description 9
- 229930091371 Fructose Natural products 0.000 claims description 8
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 8
- 239000005715 Fructose Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 235000007164 Oryza sativa Nutrition 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 235000009566 rice Nutrition 0.000 claims description 7
- 235000000346 sugar Nutrition 0.000 claims description 5
- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 claims description 4
- 235000014676 Phragmites communis Nutrition 0.000 claims description 4
- 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 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 2
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical group O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 241000209094 Oryza Species 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- PKAUICCNAWQPAU-UHFFFAOYSA-N 2-(4-chloro-2-methylphenoxy)acetic acid;n-methylmethanamine Chemical compound CNC.CC1=CC(Cl)=CC=C1OCC(O)=O PKAUICCNAWQPAU-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 235000011149 sulphuric acid Nutrition 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 229910020810 Sn-Co Inorganic materials 0.000 description 4
- 229910018757 Sn—Co Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 241000894007 species Species 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000005882 aldol condensation reaction Methods 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 238000000855 fermentation Methods 0.000 description 3
- 230000004151 fermentation Effects 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 239000010903 husk Substances 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910019043 CoSn Inorganic materials 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 244000273256 Phragmites communis Species 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- -1 alkyl lactate Chemical compound 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002029 lignocellulosic biomass Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004627 transmission electron microscopy 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/398—Egg yolk like
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a catalyst, a preparation method thereof and a method for preparing lactic acid by saccharide catalysis, wherein the catalyst is a siliceous biomass loaded Co-Sn catalyst, wherein the loading capacity (mass fraction) of Co is 1-20%, and the loading capacity (mass fraction) of Sn is 1-30%. Therefore, the invention utilizes the characteristic that the siliceous biomass contains natural high-activity silicon source and carbon source to realize the mutual promotion or synergy between bimetal and metal and carbon source, thereby realizing that the catalyst catalyzes saccharide to generate lactic acid in the environment of aqueous solution and further providing a new conversion path for converting saccharide into lactic acid.
Description
Technical Field
The invention relates to the field of lactic acid production, in particular to a method for preparing lactic acid by catalysis of saccharides.
Background
Biomass as a sustainable green carbon source has wide availability and huge annual output scale, has great potential to supplement fossil-derived carbon, has become an important direction of global development for clean and efficient conversion of biomass into energy and chemicals, and how to use lignocellulosic biomass resources for the preparation of high value-added chemicals has important significance in reducing fossil resource dependence and reducing CO2 emissions. Cellulose, which is the most abundant component in biomass resources, can be converted into various high-value platform chemicals, wherein Lactic Acid (LA), which is one of three world-recognized organic acids, is an important platform chemical for producing alkyl lactate, propylene glycol, acrylic acid and polylactic acid, among chemicals synthesized from biomass, is a high-potential multifunctional platform compound.
The industrial lactic acid production method mainly comprises a fermentation method and a synthesis method, wherein the fermentation method is a mature lactic acid production method which is characterized by simple process, sufficient raw materials and early development, but has long period and can only realize intermittent or semi-continuous production, and the quality of domestic fermentation lactic acid can not reach the international standard. The chemical method can realize large-scale continuous production of lactic acid, but the raw materials are generally toxic and do not meet the green chemical requirements, thus being unfavorable for safe production.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the present invention proposes a method for preparing lactic acid by catalysis of saccharides.
According to the catalyst for catalyzing lactic acid by using the saccharides, which is provided by the embodiment of the invention, the catalyst is a siliceous biomass-supported Co-Sn catalyst, and the siliceous biomass-supported Co-Sn catalyst is formed by supporting Co and Sn on a carrier in proportion, wherein the loading amount (mass fraction) of Co is 1-20%, and the loading amount (mass fraction) of Sn is 1-30%.
According to some embodiments of the invention, the loading (mass fraction) of Co is 5% and the loading (mass fraction) of Sn is 3%.
According to some embodiments of the invention, the siliceous biomass comprises rice hulls, oat hulls, and reed.
A method of preparing a catalyst according to the second aspect of the embodiment of the present invention, the method comprising the steps of:
mixing silicon-containing biomass and a Co source, and performing hydrothermal reaction;
mixing the solution after the hydrothermal reaction with a Sn source, removing solvent water, drying to obtain solid powder,
and pyrolyzing the obtained solid powder under the protection gas flow to obtain the Co-Sn catalyst loaded by the siliceous biomass.
According to some embodiments of the invention, the Co source is CoCl2.6H2O and the Sn source is SnCl4.5H2O.
A method of preparing lactic acid by catalysis of saccharides according to a third aspect of embodiments of the present invention, the method comprising the steps of:
adding saccharides, water and a catalyst into a closed container, and carrying out high-temperature reaction under a protective atmosphere to obtain a lactic acid-containing solution after the reaction is finished, wherein the catalyst is a siliceous biomass loaded Co-Sn catalyst, and the loading amount (mass fraction) of Co is 1-20%, and the loading amount (mass fraction) of Sn is 1-30%.
According to some embodiments of the invention, the saccharide, water and catalyst are added into a closed container, and the protective atmosphere pressure ranges from 2MPa to 8MPa when the high temperature reaction is performed under the protective atmosphere.
According to some embodiments of the invention, the saccharide, water and catalyst are added to a closed vessel at a reaction temperature of 220-280 ℃ when the high temperature reaction is performed under a protective atmosphere.
In some embodiments according to the invention, the saccharide comprises cellulose, cellobiose, glucose, fructose.
The beneficial effects are that:
the invention utilizes the characteristic that the siliceous biomass contains a natural high-activity silicon source and a carbon source to realize the mutual promotion or synergy between bimetal and metal and carbon source, thereby realizing that the siliceous biomass loaded Co-Sn catalyst catalyzes saccharides to generate lactic acid in the environment of aqueous solution, and further providing a new conversion path for converting the saccharides into the lactic acid.
The catalyst adopted by the invention takes biomass as a carrier, so that the resource utilization of waste biomass (especially siliceous biomass) can be promoted.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 is a transmission electron microscopy image of an example 3% Sn-5% Co/RHC catalyst according to the present invention;
FIG. 2 is an XRD pattern for example 3% Sn-5% Co/RHC catalyst according to the invention.
Detailed Description
Embodiments of the present invention will be described in detail below, by way of example with reference to the accompanying drawings.
A method for preparing lactic acid by catalysis of saccharides according to an embodiment of the present invention is described below with reference to fig. 1 to 2.
The method for preparing lactic acid by catalysis of saccharides comprises the following steps:
adding saccharides, water and a catalyst into a high-pressure reaction kettle, reacting under the conditions of nitrogen serving as a protective atmosphere and a reaction temperature ranging from 220 ℃ to 280 ℃ under the pressure ranging from 2MPa to 8MPa, and cooling after the reaction is finished to obtain a solution containing lactic acid; the saccharide comprises cellulose, cellobiose, glucose and fructose, the catalyst can be a siliceous biomass loaded Co-Sn catalyst, and is prepared by loading Co and Sn on a siliceous biomass carrier according to a certain proportion, wherein the mass ratio of Co to Sn is 1:0.2-1:20, the loading amount (mass fraction) of Co is 1-20%, and the loading amount (mass fraction) of Sn is 1-30%.
Specifically, a series of reactions of sugar, water and catalyst can occur in a high-pressure reaction kettle, in the process of converting cellulose into lactic acid by taking cellulose as an example, the reaction is firstly subjected to a cellulose hydrolysis reaction to generate glucose, the reaction is usually carried out under an acidic condition, but under a subcritical water phase condition, H+ generated by water electrolysis can also catalyze cellulose hydrolysis, then glucose undergoes an isomerization reaction under a Lewis acid or alkaline condition to generate fructose, and the fructose further undergoes a Retrol-aldol condensation reaction under the Lewis acid or alkaline condition to generate a C3 intermediate, and further hydration to generate lactic acid.
In the above reaction, sn is present in combination with SiO 2 The combination of the carrier can obviously influence the electronic state of Sn species to form Sn with non-integer valence state δ+ And SnO x Species which can provide strong alkaline sites for the catalyst, efficiently catalyze glucose isomerism and fructose Retro-aldol condensation to generate C3 products, and further facilitate the generation of lactic acid; meanwhile, the combination of Sn and Co can also obviously increase the non-integer value SnO in the catalyst x The species, thereby increasing the basicity of the catalyst, promotes glucose isomerization and fructose Retro-aldol condensation reactions, and provides the basic site for catalyzing the conversion of glucose to C3 molecules.
In addition, the siliceous biomass such as wheat hulls and rice hulls contains a large amount of plant silicic acid (amorphous silica), the Si species have high activity and are more easily interacted with metal, and H generated in the pyrolysis process of an organic carbon source after hydrothermal reaction of the siliceous biomass 2 、CH 4 Reducing gases such as CO and the like can reduce metal ions in situ, and the existence of biomass charcoal can inhibit agglomeration of nano silicon dioxide in siliceous biomass, so that catalysis can be improvedThe stability of the catalyst is improved, and the problems that the catalyst is poor in stability and difficult to reuse in the cellulose conversion process are solved.
Therefore, the invention utilizes the characteristic that the siliceous biomass contains a natural high-activity silicon source and a carbon source to realize the mutual promotion or synergy between bimetal and metal and carbon source, thereby realizing that the siliceous biomass loaded Co-Sn catalyst catalyzes saccharides to generate lactic acid in the environment of aqueous solution, and further providing a new conversion path for converting the saccharides into the lactic acid.
The catalyst adopted in the method takes biomass as a carrier, so that the resource utilization of waste biomass (especially siliceous biomass) can be promoted; meanwhile, the method uses water as a solvent, thereby avoiding the problem of environmental pollution when an organic solvent is adopted.
H generated in pyrolysis process of organic carbon source after hydrothermal reaction of siliceous biomass 2 、CH 4 Reducing gases such as CO and the like can reduce metal ions in situ, so that agglomeration of nano silicon dioxide in siliceous biomass can be inhibited, and stability of the catalyst is improved.
Further, based on the above examples, the loading (mass fraction) of Co was 5% and the loading (mass fraction) of Sn was 3%, and specifically, according to the results of example 2, it is known that the yield of lactic acid when 3% Sn-5% Co/RHC catalyzes cellulose to prepare lactic acid was as high as 66.5%, so that the yield of lactic acid prepared by catalysis of saccharides was greatly improved, and industrial production was facilitated.
Referring to fig. 1 and fig. 2, a method for preparing a catalyst according to an embodiment of the present invention, wherein the catalyst refers to: the catalyst is a siliceous biomass loaded Co-Sn catalyst, the siliceous biomass comprises any one or the combination of more than two of rice hulls, oat hulls and reeds, and the preparation method comprises the following steps: biomass containing silicon and CoCl 2 ·6H 2 Mixing O solution, performing hydrothermal reaction, and mixing the solution after the hydrothermal reaction with SnCl 4 ·5H 2 Mixing the O solution, removing solvent water, drying to obtain solid powder, and pyrolyzing the solid powder under the protection gas flow to obtain silicon-containing materialBiomass supported Co-Sn catalyst.
More specifically, 5.0g of the support was added to a 100mL hydrothermal kettle, and a quantity of CoCl was added 2 ·6H 2 O is dissolved in 50mL of deionized water, then added into the hydrothermal kettle continuously, mixed uniformly and heated for 12h at 200 ℃. Cooled to room temperature and transferred directly to a round bottom flask, a small beaker was taken and dissolved with 10mL of water to a certain amount of SnCl 4 ·5H 2 O was slowly dropped into the round bottom flask, 50mL of deionized water was added thereto, the mixture was stirred at 45℃for 12 hours, the solvent water was removed by rotary evaporation, and the mixture was dried at 105℃overnight, and then the solid powder was dried at N 2 Pyrolysis in stream at 600℃for 2h, cooling to room temperature, and then cooling to room temperature with 1%O 2 /N 2 Purging for 30min to obtain the Co-Sn bimetallic catalyst loaded by the siliceous biomass.
Thus, the method loads Co through hydrothermal process and then loads Sn, so that Co is combined with active Si in siliceous biomass and pure SiO 2 The carrier is different in that active Si in the biomass can promote Sn and Co to combine to form CoSn alloy (figure 2), and the combination of Co, sn and C is influenced, and organic carbon in the biomass carrier forms a carbon layer to wrap metal in the process, so that the agglomeration and loss of the active metal can be obviously inhibited, and the conversion of saccharides such as cellulose and the like into lactic acid is promoted.
Example 1
Preparation of Sn-Co bimetallic catalyst (taking x% Sn-5% Co/RHC as an example) supported by rice husk as carrier
5.0g of rice hulls passing through a 80 mesh screen are added to a 100mL hydrothermal kettle, and 1.06g of CoCl is added 2 ·6H 2 O is dissolved in 50mL deionized water, and after being evenly dissolved by ultrasonic, the O is continuously added into the hydrothermal kettle to be evenly mixed, and the mixture is heated for 12 hours at 200 ℃. Cooled to room temperature and transferred directly to a round bottom flask, a small beaker was taken and dissolved with 10mL of water to a certain amount of SnCl 4 The round bottom flask was slowly dropped, 50mL of deionized water was added thereto, and after stirring at 45 ℃ for 12 hours, the solvent water was removed by spin evaporation, and dried overnight at 105 ℃. The solid powder is then subjected to N 2 Pyrolyzing at 600deg.C for 2 hr, cooling to room temperatureAfter this time, the catalyst was purged with 1% O2/N2 for 30min to give an x% Sn-5% Co/RHC catalyst.
TABLE 1 preparation of Sn-Co/RHC catalysts with different Sn/Co ratios
Example 2.
Preparation of lactic acid by catalyzing cellulose with Sn-Co/RHC with different Sn/Co ratios
50mg of cellulose, 50mg of catalyst and 10mL of water as a solvent were charged into a 25mL autoclave, followed by N 2 The reaction was carried out at a pressure of 4MPa and a temperature of 250℃for 1 hour, cooled after the completion of the reaction, and the reaction mixture was filtered and used for liquid phase detection (HPLC, waters 1525, shodex RI-201H detector, bio-Rad Aminex HPX-87H column, using 0.005M H2SO4 as mobile phase). The results are shown in Table 2:
TABLE 2 preparation of lactic acid by Sn-Co/RHC catalyzed cellulose with different Sn/Co ratios
Example 3
Preparation of lactic acid by catalyzing various saccharides with 3% Sn-5% Co/RHC
50mg of substrate, 50mg of 3% Sn-5% Co/RHC catalyst and 10mL of water as solvent are added into a 25mL autoclave, and the mixture is put into N 2 The reaction was carried out at a pressure of 4MPa and a temperature of 250℃for 1 hour, cooled after the completion of the reaction, and the reaction mixture was filtered and used for liquid phase detection (HPLC, waters 1525, shodex RI-201H detector, bio-Rad Aminex HPX-87H column, using 0.005M H2SO4 as mobile phase). The results are shown in Table 3:
TABLE 3 20% Sn-10% Co/SiO 2 Catalytic production of lactic acid from a plurality of sugars
| Substrate(s) | Lactic acid yield/% |
| Cellulose | 66.5 |
| Cellobiose | 58.8 |
| Glucose | 60.7 |
| Fructose | 69.8 |
Example 4
Preparation of lactic acid by catalyzing cellulose with different siliceous biomass carriers loaded with 3% Sn-5% Co catalyst
50mg of cellulose and 50mg of siliceous biomass carrier loaded with 3% Sn-5% Co catalyst are added into a 25mL high-pressure reaction kettle, 10mL of water is taken as a solvent, and the mixture is added into a reactor under the condition of N 2 The reaction was carried out at a pressure of 4MPa and a temperature of 250℃for 1 hour, cooled after the completion of the reaction, and the reaction mixture was filtered and used for liquid phase detection (HPLC, waters 1525, shodex RI-201H detector, bio-Rad Aminex HPX-87H column, using 0.005M H2SO4 as mobile phase). The results are shown in Table 4:
TABLE 4 preparation of lactic acid by catalyzing cellulose with different siliceous Biomass carriers loaded with 3% Sn-5% Co catalyst
| Carrier body | Lactic acid yield/% |
| Rice husk | 66.5 |
| Oat hull | 60.7 |
| Reed | 48.2 |
Example 5
Effect of different N2 pressures on conversion of cellulose to lactic acid
50mg of cellulose, 50mg of 3% Sn-5% Co/RHC catalyst and 10mL of water as solvent are added into a 25mL high-pressure reaction kettle, and the mixture is added into N 2 The reaction was carried out at a pressure of 0.5 to 8MPa and a temperature of 250℃for 1 hour, and after the completion of the reaction, the reaction mixture was cooled and filtered and used for liquid phase detection (HPLC, waters 1525, shodex RI-201H detector, bio-Rad Aminex HPX-87H column, using 0.005M H2SO4 as mobile phase). The results are shown in Table 5:
TABLE 5 influence of different reaction Hydrogen pressures on the conversion of cellulose to lactic acid
| N 2 Pressure (MPa) | Lactic acid yield/% |
| 0.5 | 32.1 |
| 1 | 40.4 |
| 2 | 50.7 |
| 3 | 58.2 |
| 4 | 66.5 |
| 5 | 66.8 |
| 6 | 60.2 |
| 7 | 55.4 |
| 8 | 51.1 |
Example 6.
Effects of different reaction temperatures on conversion of cellulose to lactic acid
50mg of cellulose, 50mg of 3% Sn-5% Co/RHC catalyst and 10mL of water are added into a 25mL autoclave, the mixture is reacted for 1 hour under the condition that the N2 pressure is 4MPa and the temperature is 150-300 ℃, the mixture is cooled after the reaction is finished, and the reaction solution is filtered and used for liquid phase detection (HPLC, waters 1525, shodex RI-201H detector, bio-Rad Aminex HPX-87H chromatographic column, and 0.005M H2SO4 is used as a mobile phase). The results are shown in Table 6:
TABLE 6 influence of different reaction temperatures on the conversion of cellulose to lactic acid
| Temperature (. Degree. C.) | Lactic acid yield/% |
| 150 | 19.9 |
| 180 | 25.5 |
| 200 | 30.2 |
| 220 | 42.6 |
| 240 | 63.3 |
| 250 | 66.5 |
| 260 | 55.7 |
| 280 | 48.8 |
| 300 | 40.2 |
In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", "axial", "radial", "circumferential", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the device or element being referred to must have a specific orientation, be configured and operated in a specific orientation, and therefore should not be construed as limiting the present invention.
In the description of the present specification, reference to the terms "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples.
While embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that: many changes, modifications, substitutions and variations may be made to the embodiments without departing from the spirit and principles of the invention, the scope of which is defined by the claims and their equivalents.
Claims (9)
1. The catalyst is used for catalyzing lactic acid as saccharides, and is characterized by being a siliceous biomass-supported Co-Sn catalyst which is formed by supporting Co and Sn on a carrier in proportion, wherein the supporting amount (mass fraction) of Co is 1-20%, and the supporting amount (mass fraction) of Sn is 1-30%.
2. A catalyst according to claim 1, characterized in that the Co loading (mass fraction) is 5% and the Sn loading (mass fraction) is 3%.
3. The catalyst of claim 1, wherein the siliceous biomass comprises rice hulls, oat hulls, and reed.
4. A process for preparing a catalyst according to any one of claims 1 to 3, comprising the steps of:
mixing silicon-containing biomass and a Co source, and performing hydrothermal reaction;
mixing the solution after the hydrothermal reaction with a Sn source, removing solvent water, drying to obtain solid powder,
and pyrolyzing the obtained solid powder under the protection gas flow to obtain the Co-Sn catalyst loaded by the siliceous biomass.
5. The method for preparing a catalyst according to claim 4, wherein the Co source is CoCl2.6H2O and the Sn source is SnCl4.5H2O.
6. A method for the catalytic production of lactic acid from a saccharide, the method comprising the steps of:
adding saccharides, water and a catalyst into a closed container, and carrying out high-temperature reaction under a protective atmosphere to obtain a solution containing lactic acid after the reaction is finished, wherein the catalyst adopts the catalyst as claimed in any one of claims 1 to 3.
7. The method for preparing lactic acid by catalysis of sugar according to claim 6, wherein the pressure of the protective atmosphere when the reaction is carried out at high temperature under the protective atmosphere is in the range of 2MPa to 8MPa.
8. The method for preparing lactic acid by catalysis of sugar according to claim 6, wherein the reaction temperature is 220-280 ℃ when the reaction is carried out under a protective atmosphere by adding the sugar, water and catalyst into a closed container.
9. The method for preparing lactic acid by catalysis according to claim 6, wherein the saccharide comprises cellulose, cellobiose, glucose, fructose.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310496566.7A CN116618058A (en) | 2023-05-05 | 2023-05-05 | Catalyst, preparation method thereof and method for preparing lactic acid by catalysis of saccharides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310496566.7A CN116618058A (en) | 2023-05-05 | 2023-05-05 | Catalyst, preparation method thereof and method for preparing lactic acid by catalysis of saccharides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116618058A true CN116618058A (en) | 2023-08-22 |
Family
ID=87612555
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310496566.7A Pending CN116618058A (en) | 2023-05-05 | 2023-05-05 | Catalyst, preparation method thereof and method for preparing lactic acid by catalysis of saccharides |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116618058A (en) |
-
2023
- 2023-05-05 CN CN202310496566.7A patent/CN116618058A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107365286B (en) | Method for synthesizing 2, 5-furandicarboxylic acid | |
| CN107365287B (en) | A method of synthesis 2,5- furandicarboxylic acid | |
| CN111875566B (en) | Method for preparing 2, 5-dimethylfuran | |
| CN110270366B (en) | Preparation method of high-activity catalyst for catalyzing glucose isomerization | |
| CN112121863B (en) | Catalyst for catalytic transfer hydrogenation and preparation method and application thereof | |
| CN111377890B (en) | Method for producing 2,5-furandicarboxylic acid from 5-hydroxymethylfurfural | |
| CN111054392B (en) | Metal-solid acid double-center catalyst and application thereof in preparation of furfuryl alcohol by catalyzing xylose dehydration-hydrogenation | |
| CN113117688A (en) | MOF precursor molybdenum-nickel catalyst, preparation method thereof and application thereof in lignin degradation | |
| CN111514895A (en) | Preparation method and application of transition bimetallic catalyst | |
| CN111408392A (en) | Cobalt-nitrogen co-doped porous carbon material catalyst and preparation method and application thereof | |
| CN114057554B (en) | Method for preparing 2, 5-hexanedione through lignocellulose catalytic hydrogenation | |
| CN107245065A (en) | A kind of method that catalytic hydrogenation ethyl levulinate prepares valerolactone | |
| CN113527703A (en) | Metal carbon-based coordination polymer, preparation method and application thereof in synthesis of 2, 5-furandimethanol | |
| CN115138392B (en) | Multifunctional biochar catalyst rich in oxygen-containing functional groups and preparation method thereof | |
| CN116618058A (en) | Catalyst, preparation method thereof and method for preparing lactic acid by catalysis of saccharides | |
| CN109704917B (en) | Process for chemically converting corncob furfural residues into bioethanol | |
| CN109400557B (en) | Method for preparing furoic acid and 5-hydroxymethyl furoic acid by using biomass | |
| Qiu et al. | Efficient conversion of biomass to 5-hydroxymethylfurfural via hydrothermal liquefaction: Mechanisms, catalysts and potential applications | |
| CN111423398A (en) | Method for preparing gamma-valerolactone from levulinic acid | |
| TW201402528A (en) | Method for producing isopropanol by catalytic conversion of cellulose | |
| CN113509931B (en) | Cu (copper) alloy 2 Preparation of O/CuO@CA photocatalyst and application of O/CuO@CA photocatalyst in synthesis of lactic acid by photocatalytic oxidation of xylose | |
| CN115322083B (en) | Method for preparing 2, 5-hexanedione from biomass raw material | |
| CN112062673B (en) | Method for directionally synthesizing methyl lactate by catalytically converting fructose by one-pot method | |
| Du et al. | catalytic conversion of 5-hydroxymethylfurfural and fructose to 5-ethoxymethylfurfural over sulfonated biochar catalysts | |
| CN114749211B (en) | Sulfonic carbon microsphere and preparation method and application thereof |
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 |