CN112264051A - Preparation method of solid acid catalyst for cellulose hydrolysis and product thereof - Google Patents
Preparation method of solid acid catalyst for cellulose hydrolysis and product thereof Download PDFInfo
- Publication number
- CN112264051A CN112264051A CN202011107865.XA CN202011107865A CN112264051A CN 112264051 A CN112264051 A CN 112264051A CN 202011107865 A CN202011107865 A CN 202011107865A CN 112264051 A CN112264051 A CN 112264051A
- Authority
- CN
- China
- Prior art keywords
- acid catalyst
- solid acid
- zirconium
- heating
- product
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 239000011973 solid acid Substances 0.000 title claims abstract description 50
- 229920002678 cellulose Polymers 0.000 title claims abstract description 29
- 239000001913 cellulose Substances 0.000 title claims abstract description 29
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 26
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 34
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 229960000583 acetic acid Drugs 0.000 claims abstract description 17
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 17
- 229910052742 iron Inorganic materials 0.000 claims abstract description 17
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 17
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 15
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 13
- 239000011593 sulfur Substances 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims description 33
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 238000001816 cooling Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 102000020897 Formins Human genes 0.000 claims description 6
- 108091022623 Formins Proteins 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000013110 organic ligand Substances 0.000 claims description 6
- 239000010453 quartz Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 6
- 239000012498 ultrapure water Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 3
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 239000003575 carbonaceous material Substances 0.000 abstract description 3
- 230000005389 magnetism Effects 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 239000013384 organic framework Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 241000282414 Homo sapiens Species 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- LWFUFLREGJMOIZ-UHFFFAOYSA-N 3,5-dinitrosalicylic acid Chemical compound OC(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O LWFUFLREGJMOIZ-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004073 vulcanization Methods 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
-
- 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
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
-
- 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
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
- B01J37/12—Oxidising
-
- 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
- B01J37/20—Sulfiding
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biotechnology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Molecular Biology (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a solid acid catalyst for cellulose hydrolysis and a product thereof. The solid acid catalyst is prepared by firstly preparing an iron and zirconium bimetal organic framework material and then carrying out sectional carbonization under inert gasObtaining a carbon material modified with iron and zirconium, then sulfurizing by subliming sulfur to obtain a sulfur-containing carrier, followed by H2O2-carrying out an oxidation reaction in a glacial acetic acid solution to obtain a solid acid catalyst. The acidity of the solid acid catalyst is obviously improved through the modification of iron and zirconium, and the solid acid catalyst is endowed with certain magnetism, so that the hydrolysis conversion rate of cellulose is improved, and the stability of the solid acid catalyst is also improved.
Description
Technical Field
The invention relates to the field of solid acid catalysts, in particular to a preparation method of a solid acid catalyst for cellulose hydrolysis and a product thereof.
Background
The global exhaustion of fossil fuel resources and environmental problems have led to the exploration of renewable raw materials and sustainable development, and the use of fossil fuels has brought unprecedented pressure to the living environment of human beings and seriously threatens the survival of human beings, and in order to alleviate the environmental and energy crisis, renewable energy has received wide attention from people, among which, cellulose is the most abundant organic molecule, and is converted into biochemical products and biofuels by hydrolysis.
In order to overcome the problems, a carbon-based solid acid catalyst is adopted to be applied to reactions such as cellulose hydrolysis, esterification and the like, and has the advantages of low price, easy separation, reusability, small environmental pollution and the like, so that the carbon-based solid acid catalyst is widely concerned.
Hara et al heated naphthalene in concentrated sulfuric acid (> 96%) (200-300 ℃ C.) to obtain a carbon-based solid acid for the first time. Sulfonic groups are introduced into carbon-based solid acid, and a method of sulfonating by concentrated sulfuric acid or fuming sulfonic acid is mostly adopted, but a large amount of waste acid is generated by sulfonation, so that the method is harmful to the environment and corrodes equipment, and gases harmful to human bodies can be generated in the sulfonation process.
Therefore, in view of the above, it is desired to develop a novel carbon-based solid acid catalyst which has not only good catalytic performance but also good stability, and which does not pollute the environment and reduces the production cost.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a method for preparing a solid acid catalyst for cellulose hydrolysis and a product thereof, aiming at the defects in the prior art. The solid acid catalyst is prepared by firstly preparing an iron and zirconium bimetallic organic framework material, then carrying out sectional carbonization under inert gas to obtain an iron and zirconium modified carbon material, then carrying out sulfur sublimation vulcanization to obtain a sulfur-containing carrier, and then carrying out H reaction on the sulfur-containing carrier2O2-carrying out an oxidation reaction in a glacial acetic acid solution to obtain a solid acid catalyst. Wherein the acidity of the solid acid catalyst is significantly improved by modification with iron and zirconium, andand the solid acid catalyst is endowed with certain magnetism, so that the hydrolysis conversion rate of cellulose is improved, and the stability of the solid acid catalyst is improved, therefore, the solid acid catalyst is an ideal material for cellulose hydrolysis.
The invention adopts the following technical scheme:
a method for preparing a solid acid catalyst for cellulose hydrolysis, the method comprising the steps of:
1) adding an iron source, a zirconium source and an organic ligand into an organic solvent, magnetically stirring for 2-5 hours, transferring the mixed solution into a 100mL high-pressure reaction kettle with a polytetrafluoroethylene lining, and continuously heating for 18-24 hours at the temperature of 100-130 ℃; naturally cooling to room temperature, washing the obtained suspension with dimethylformamide, absolute ethyl alcohol and ultrapure water respectively, and washing for 3-5 times; drying in a vacuum drying oven at 50-70 ℃ overnight; obtaining a material A;
2) placing the material A obtained in the step (1) in a quartz boat, and carrying out reaction at 1-3 ℃ for min under inert gas-1Heating to 280-320 ℃ at a heating rate, keeping the temperature for 5-7 hours, and then heating to 2-4 ℃ for min-1Heating to 400-600 ℃ at the heating rate, calcining for 2-4 h, and then cooling to room temperature to obtain a product B;
3) reacting the product B with sublimed sulfur for 4-8 h at 450-550 ℃ under the protection of nitrogen; then cooling to room temperature to obtain a sulfur-containing carrier, and then using H at 20-30 DEG C2O2And oxidizing the glacial acetic acid solution for 3-6 h, cooling to room temperature, filtering, washing with boiling water to be neutral, and drying to obtain the solid acid catalyst.
Preferably, in step (1), the iron source: a zirconium source: the mass ratio of the organic ligand is 1: 0.5-1.0: 1.0 to 2.0.
Preferably, in the step (1), the iron source is one or more of ferric chloride, ferric nitrate and ferric acetate; the zirconium source is one or more of zirconium nitrate, zirconium chloride and zirconium oxychloride.
Preferably, in the step (1), the organic solvent is one or more selected from dimethylformamide, anhydrous methanol and anhydrous ethanol; the organic ligand is terephthalic acid or 2-methylimidazole.
Preferably, in the step (2), the inert gas is He or Ar.
Preferably, in the step (3), the mass ratio of the product B to the sublimed sulfur is 1: 1-3.
Preferably, in step (3), the sulfur-containing support is reacted with H2O2The solid-to-liquid ratio of the glacial acetic acid solution is 1:50 (m) (g) to v (ml); wherein H2O2And the molar concentration of glacial acetic acid is 1 mol/L.
Preferably, in the step (3), the drying is carried out at 60-80 ℃ for 12-24 h.
The invention also provides a technical scheme that the solid acid catalyst for cellulose hydrolysis is prepared based on the preparation method.
Another technical solution of the present invention is based on the use of a solid acid catalyst for cellulose hydrolysis as described above, for cellulose hydrolysis.
The preparation method of the solid acid catalyst for cellulose hydrolysis and the product thereof provided by the invention have the following technical effects:
(1) the carbon material has an excellent porous structure, the acidity of the solid acid catalyst is obviously improved due to the existence of the iron and the zirconium, the catalytic activity and the stability of the catalyst are obviously improved due to the synergistic effect of the iron and the zirconium, and the solid acid catalyst is endowed with certain magnetism due to the fact that the iron and the zirconium contain partial oxides, so that the stability of the solid acid catalyst is improved.
(2) By sulfurization with sublimed sulfur and incorporation of H2O2The oxidation of glacial acetic acid avoids the pollution to the environment and the corrosion to equipment when adopting concentrated sulfuric acid for oxidation, and obviously reduces the production cost.
(3) Through sectional carbonization, the internal pore structure of the metal organic framework is fully reserved, the specific surface area is improved, and the catalytic performance of the solid acid catalyst is further improved.
(4) The preparation method is simple and easy to control, and the prepared product has excellent performance and is beneficial to industrial production.
In conclusion, the solid acid catalyst for cellulose hydrolysis prepared by the invention has excellent catalytic activity and is an ideal material for cellulose hydrolysis.
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 with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. The components of the embodiments of the present invention generally shown may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the 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.
Example 1
A method for preparing a solid acid catalyst for cellulose hydrolysis, the method comprising the steps of:
1) adding 2g of ferric nitrate, 1.6g of zirconium nitrate and 3g of terephthalic acid into 50mL of dimethylformamide, magnetically stirring for 4 hours, transferring the mixed solution into a 100mL of polytetrafluoroethylene-lined high-pressure reaction kettle, and continuously heating for 20 hours at 120 ℃; naturally cooling to room temperature, washing the obtained suspension with dimethylformamide, absolute ethyl alcohol and ultrapure water respectively, and washing for 4 times; drying in a vacuum drying oven at 60 ℃ overnight; obtaining a material A;
2) putting the material A obtained in the step (1) into a quartz boat, and carrying out reaction at 2 ℃ for min in He atmosphere-1Heating to 300 ℃ at a heating rate, keeping the temperature for 6 hours, and then heating to 3 ℃ for min-1Heating to 550 ℃ at the heating rate, calcining for 3h, and then cooling to room temperature to obtain a product B;
3) 2g of product B and 4g of sublimed sulphur were placed under nitrogen blanketReacting for 6 hours at 500 ℃; then cooling to room temperature to obtain sulfur-containing carrier, and then reacting with H at 25 deg.C2O2Oxidizing glacial acetic acid solution at solid-to-liquid ratio of m (g) to V (mL) in a ratio of 1:50 for 4H, wherein H2O2And glacial acetic acid, cooling to room temperature, filtering, washing with boiling water to neutrality, and drying at 70 deg.C for 20 hr to obtain solid acid catalyst.
Example 2
A method for preparing a solid acid catalyst for cellulose hydrolysis, the method comprising the steps of:
1) adding 2g of ferric chloride, 2g of zirconium chloride and 4g of 2-methylimidazole into 50mL of anhydrous methanol, magnetically stirring for 5 hours, transferring the mixed solution into a 100mL of polytetrafluoroethylene-lined high-pressure reaction kettle, and continuously heating for 18 hours at the temperature of 130 ℃; naturally cooling to room temperature, washing the obtained suspension with dimethylformamide, absolute ethyl alcohol and ultrapure water respectively, and washing for 5 times; drying in a vacuum drying oven at 70 ℃ overnight;
2) putting the material A obtained in the step (1) into a quartz boat, and carrying out reaction at 3 ℃ for min in Ar atmosphere-1Heating to 320 ℃ at a heating rate, keeping the temperature for 5 hours, and then heating to 4 ℃ for min-1Heating to 600 ℃ at the heating rate, calcining for 2h, and then cooling to room temperature to obtain a product B;
3) 2g of the product B and 6h of sublimed sulfur are reacted for 4h at 550 ℃ under the protection of nitrogen; then cooling to room temperature to obtain sulfur-containing carrier, and then reacting with H at 30 deg.C2O2Oxidizing glacial acetic acid solution at solid-to-liquid ratio of m (g) to V (mL) in a ratio of 1:50 for 6H, wherein H2O2And glacial acetic acid, cooling to room temperature, filtering, washing with boiling water to neutrality, and drying at 80 deg.C for 12 hr to obtain solid acid catalyst.
Example 3
A method for preparing a solid acid catalyst for cellulose hydrolysis, the method comprising the steps of:
1) adding 2g of iron acetate, 1g of zirconium oxychloride and 2g of terephthalic acid into 50mL of absolute ethyl alcohol, magnetically stirring for 2h, transferring the mixed solution into a 100mL of polytetrafluoroethylene-lined high-pressure reaction kettle, and continuously heating for 24h at 100 ℃; naturally cooling to room temperature, washing the obtained suspension with dimethylformamide, absolute ethyl alcohol and ultrapure water respectively, and washing for 3 times; drying in a vacuum drying oven at 50 ℃ overnight; obtaining a material A;
2) putting the material A obtained in the step (1) into a quartz boat, and carrying out reaction at 1 ℃ for min in He atmosphere-1Heating to 280 ℃ at a heating rate, keeping the temperature for 7 hours, and then heating to 2 ℃ for min-1Heating to 400 ℃ at the heating rate, calcining for 4h, and then cooling to room temperature to obtain a product B;
3) 2g of the product B and 2g of sublimed sulfur are reacted for 8 hours at 450 ℃ under the protection of nitrogen; then cooling to room temperature to obtain sulfur-containing carrier, and then reacting with H at 20 deg.C2O2Oxidizing glacial acetic acid solution at solid-to-liquid ratio of m (g) to V (mL) in a ratio of 1:50 for 6H, wherein H2O2And glacial acetic acid, cooling to room temperature, filtering, washing with boiling water to neutrality, and drying at 60 deg.C for 24 hr to obtain solid acid catalyst.
Comparative example 1
In step (1), a metal organic framework was prepared using only ferric chloride having a mass of 3.6g, and the other steps and conditions were the same as in example 1.
Comparative example 2
In step (1), a metal organic framework in which the mass of ferric chloride was 3.6g was prepared using only zirconium nitrate, and the other steps and conditions were the same as in example 1.
Comparative example 3.
A method for preparing a solid acid catalyst for cellulose hydrolysis, the method comprising the steps of:
1) adding 2g of ferric nitrate, 1.6g of zirconium nitrate and 3g of terephthalic acid into 50mL of dimethylformamide, magnetically stirring for 4 hours, transferring the mixed solution into a 100mL of polytetrafluoroethylene-lined high-pressure reaction kettle, and continuously heating for 20 hours at 120 ℃; naturally cooling to room temperature, washing the obtained suspension with dimethylformamide, absolute ethyl alcohol and ultrapure water respectively, and washing for 4 times; drying in a vacuum drying oven at 60 ℃ overnight; obtaining a material A;
2) putting the material A obtained in the step (1) into a quartz boat, and carrying out reaction at 3 ℃ for min in He atmosphere-1Heating to 550 ℃ at the heating rate, calcining for 9h, and then cooling to room temperature to obtain a product B;
3) 2g of the product B and 4g of sublimed sulfur are reacted for 6 hours at 500 ℃ under the protection of nitrogen; then cooling to room temperature to obtain sulfur-containing carrier, and then reacting with H at 25 deg.C2O2Oxidizing glacial acetic acid solution at solid-to-liquid ratio of m (g) to V (mL) in a ratio of 1:50 for 4H, wherein H2O2And glacial acetic acid, cooling to room temperature, filtering, washing with boiling water to neutrality, and drying at 70 deg.C for 20 hr to obtain solid acid catalyst.
The solid acid catalysts of examples 1-3 and comparative examples 1-3 were used in cellulose hydrolysis experiments. The specific method comprises the following steps:
accurately weighing 0.2g of solid acid catalyst and 10g of pretreated cellulose, placing the solid acid catalyst and the pretreated cellulose in a high-pressure reaction kettle, adding 10mL of distilled water, and hydrolyzing for 4 hours at 160 ℃ under magnetic stirring to obtain cellulose hydrolysate. The total reducing sugar yield is determined by a 3, 5-dinitrosalicylic acid (DNS) method.
Specific test results are shown in table 1:
TABLE 1 catalytic conversion and selectivity of the solid acid catalysts of examples 1-3 and comparative examples 1-3
| Novel catalyst | Catalyst used after 10 times | |
| Reducing sugar yield (%) | Reducing sugar yield (%) | |
| Example 1 | 92.1 | 89.4 |
| Example 2 | 90.2 | 87.1 |
| Example 3 | 91.5 | 88.3 |
| Comparative example 1 | 79.5 | 78.3 |
| Comparative example 2 | 84.3 | 79.1 |
| Comparative example 3 | 86.7 | 84.5 |
Through the comparison of the examples 1 to 3 and the comparative examples 1 to 3, the solid acid catalyst prepared by the bimetallic organic framework of iron and zirconium has excellent catalytic performance, the iron and the zirconium have synergistic effect, and the sectional carbonization also obviously improves the catalytic performance of the solid acid catalyst.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A method for preparing a solid acid catalyst for cellulose hydrolysis, which is characterized by comprising the following steps: the preparation method comprises the following steps:
1) adding an iron source, a zirconium source and an organic ligand into an organic solvent, magnetically stirring for 2-5 hours, transferring the mixed solution into a 100mL high-pressure reaction kettle with a polytetrafluoroethylene lining, and continuously heating for 18-24 hours at the temperature of 100-130 ℃; naturally cooling to room temperature, washing the obtained suspension with dimethylformamide, absolute ethyl alcohol and ultrapure water respectively, and washing for 3-5 times; drying in a vacuum drying oven at 50-70 ℃ overnight; obtaining a material A;
2) placing the material A obtained in the step (1) in a quartz boat, and carrying out reaction at 1-3 ℃ for min under inert gas-1Heating to 280-320 ℃ at a heating rate, keeping the temperature for 5-7 hours, and then heating to 2-4 ℃ for min-1Heating to 400-600 ℃ at the heating rate, calcining for 2-4 h, and then cooling to room temperature to obtain a product B;
3) reacting the product B with sublimed sulfur for 4-8 h at 450-550 ℃ under the protection of nitrogen; then cooling to room temperature to obtain a sulfur-containing carrier, and then using H at 20-30 DEG C2O2And oxidizing the glacial acetic acid solution for 3-6 h, cooling to room temperature, filtering, washing with boiling water to be neutral, and drying to obtain the solid acid catalyst.
2. The method of claim 1, wherein: in step (1), the iron source: a zirconium source: the mass ratio of the organic ligand is 1: 0.5-1.0: 1.0 to 2.0.
3. The method of claim 1, wherein: in the step (1), the iron source is one or more of ferric chloride, ferric nitrate and ferric acetate; the zirconium source is one or more of zirconium nitrate, zirconium chloride and zirconium oxychloride.
4. The method of claim 1, wherein: in the step (1), the organic solvent is one or more selected from dimethylformamide, anhydrous methanol and anhydrous ethanol; the organic ligand is terephthalic acid or 2-methylimidazole.
5. The method of claim 1, wherein: in the step (2), the inert gas is He or Ar.
6. The method of claim 1, wherein: in the step (3), the mass ratio of the product B to the sublimed sulfur is 1: 1-3.
7. The method of claim 1, wherein: in step (3), the sulfur-containing carrier is reacted with H2O2The solid-to-liquid ratio of the glacial acetic acid solution is 1:50 (m) (g) to v (ml); wherein H2O2And the molar concentration of glacial acetic acid is 1 mol/L.
8. The method of claim 1, wherein: in the step (3), the drying is carried out at 60-80 ℃ for 12-24 h.
9. A solid acid catalyst according to any one of claims 1 to 8 for use in the hydrolysis of cellulose.
10. Use of a solid acid catalyst for cellulose hydrolysis according to claim 9, characterized in that the catalyst is used for cellulose hydrolysis.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011107865.XA CN112264051B (en) | 2020-10-16 | 2020-10-16 | Preparation method of solid acid catalyst for cellulose hydrolysis and product thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011107865.XA CN112264051B (en) | 2020-10-16 | 2020-10-16 | Preparation method of solid acid catalyst for cellulose hydrolysis and product thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112264051A true CN112264051A (en) | 2021-01-26 |
| CN112264051B CN112264051B (en) | 2022-11-18 |
Family
ID=74337207
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011107865.XA Active CN112264051B (en) | 2020-10-16 | 2020-10-16 | Preparation method of solid acid catalyst for cellulose hydrolysis and product thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112264051B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117003228A (en) * | 2023-09-01 | 2023-11-07 | 南通大学 | Preparation method of zirconium-iron bimetal organic framework derivatization magnetic carbon material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015127033A1 (en) * | 2014-02-19 | 2015-08-27 | The Regents Of The University Of California | Acid, solvent, and thermal resistant metal-organic frameworks |
| CN107262149A (en) * | 2017-06-28 | 2017-10-20 | 宿州市逢源生物科技有限公司 | A kind of preparation method of cellulose hydrolysis biomass carbon based solid acid catalyst |
| CN108499579A (en) * | 2018-04-20 | 2018-09-07 | 东南大学 | The preparation of solid acid catalyst based on Zr-MOF and its application process |
-
2020
- 2020-10-16 CN CN202011107865.XA patent/CN112264051B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015127033A1 (en) * | 2014-02-19 | 2015-08-27 | The Regents Of The University Of California | Acid, solvent, and thermal resistant metal-organic frameworks |
| CN107262149A (en) * | 2017-06-28 | 2017-10-20 | 宿州市逢源生物科技有限公司 | A kind of preparation method of cellulose hydrolysis biomass carbon based solid acid catalyst |
| CN108499579A (en) * | 2018-04-20 | 2018-09-07 | 东南大学 | The preparation of solid acid catalyst based on Zr-MOF and its application process |
Non-Patent Citations (1)
| Title |
|---|
| 陈红成等: "Fe-Zr双金属－有机框架材料吸附去除水中磷酸盐", 《西南大学学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117003228A (en) * | 2023-09-01 | 2023-11-07 | 南通大学 | Preparation method of zirconium-iron bimetal organic framework derivatization magnetic carbon material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112264051B (en) | 2022-11-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111617771B (en) | Preparation method of composite metal material catalyst and application of composite metal material catalyst in preparation of 5-HMF | |
| WO2018171251A1 (en) | Solid-supported metalloporphyrin catalyst and application thereof in preparation of maleic acid | |
| US10898888B2 (en) | Preparation and application of magnetic metallic oxide cross-linked acidic polyionic liquid | |
| CN111377890B (en) | Method for producing 2,5-furandicarboxylic acid from 5-hydroxymethylfurfural | |
| CN110194730B (en) | Application of DUT-67(Zr) in preparation of methyl phenyl sulfoxide through photocatalytic oxidation of methyl phenyl sulfide | |
| CN112264051B (en) | Preparation method of solid acid catalyst for cellulose hydrolysis and product thereof | |
| CN110756203A (en) | Ni2P/Mn0.3Cd0.7S photocatalytic water splitting composite catalyst and preparation method and application thereof | |
| CN114308132B (en) | Protonated CdS-COF-366-M composite photocatalyst and preparation method thereof | |
| CN113231102B (en) | Glutaric acid selective polyacid catalyst based on micro-mesoporous Zr-MOF material and preparation method and application thereof | |
| CN113198492B (en) | Catalyst for preparing pyruvate by photocatalytic oxidation of lactate and method thereof | |
| CN114602512B (en) | Preparation method of esterification catalyst | |
| CN108855158B (en) | Preparation method and application of cobalt-ruthenium bimetallic heterogeneous catalyst | |
| CN109225312B (en) | Synthesis method of methyl p-toluenesulfonate | |
| CN108160097B (en) | Metal-free catalyst for acetylene hydrochlorination and using method thereof | |
| CN112569945B (en) | Metal-loaded dolomite catalyst for preparing ethanol by glycerol dehydration and preparation thereof | |
| CN112138673B (en) | Preparation method of bimetallic oxide material and application of bimetallic oxide material in cyclohexyl hydroperoxide decomposition reaction | |
| Takamiya et al. | Novel palladium catalyst supported on GaAs (001) passivated by ammonium sulfide | |
| JP7084378B2 (en) | Sulfur trioxide conversion method and hydrogen generation method | |
| CN112958101A (en) | Photocatalytic composite material Cr for degrading gaseous pollutants2O3-Fe2O3And preparation method and application thereof | |
| CN114763320B (en) | N (N) 2 Method for preparing glyoxalic acid by oxidizing glyoxal with O | |
| CN115090314A (en) | 0D/2D quantum dot/g-C 3 N 4 Photocatalyst and preparation method and application thereof | |
| CN115138390B (en) | Boron-nitrogen CO-doped hollow nano carbon material, preparation method thereof and photocatalytic CO (carbon monoxide) 2 Application in cycloaddition | |
| CN114890966B (en) | Catalyst for limonene epoxidation reaction | |
| CN114591476B (en) | Covalent organic framework material based on indanone framework and preparation method and application thereof | |
| CN113908873B (en) | Method for selectively oxidizing glucose by photocatalysis of carbon nitride-based photocatalyst |
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 | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20221024 Address after: 332000 West Zone, industrial park, De'an County, Jiujiang City, Jiangxi Province (opposite to Yangqiao gas station) Applicant after: DEAN COUNTY SULILONG TEXTILE CO.,LTD. Address before: Hunan University Science and Technology Park Venture Building, 186 Guyuan Road, Changsha high tech Zone, Changsha City, Hunan Province, 410205 Applicant before: HUNAN 352 ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Preparation method and product of a solid acid catalyst for cellulose hydrolysis Effective date of registration: 20230831 Granted publication date: 20221118 Pledgee: Gongqing Rural Commercial Bank branch of Limited by Share Ltd. Dean Pledgor: DEAN COUNTY SULILONG TEXTILE CO.,LTD. Registration number: Y2023980054821 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |