CN113663710B - Magnetic solid acid catalyst and application thereof in catalyzing fructose hydrolysis reaction - Google Patents
Magnetic solid acid catalyst and application thereof in catalyzing fructose hydrolysis reaction Download PDFInfo
- Publication number
- CN113663710B CN113663710B CN202110996848.4A CN202110996848A CN113663710B CN 113663710 B CN113663710 B CN 113663710B CN 202110996848 A CN202110996848 A CN 202110996848A CN 113663710 B CN113663710 B CN 113663710B
- Authority
- CN
- China
- Prior art keywords
- magnetic
- ncc
- hem
- acid catalyst
- solid acid
- 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.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 239000011973 solid acid Substances 0.000 title claims abstract description 37
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 title claims abstract description 18
- 229930091371 Fructose Natural products 0.000 title claims abstract description 18
- 239000005715 Fructose Substances 0.000 title claims abstract description 18
- 238000006460 hydrolysis reaction Methods 0.000 title abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 26
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 18
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims abstract description 16
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 15
- 239000002105 nanoparticle Substances 0.000 claims abstract description 14
- 238000003763 carbonization Methods 0.000 claims abstract description 11
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims abstract description 9
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims abstract description 9
- 239000008108 microcrystalline cellulose Substances 0.000 claims abstract description 9
- 229940016286 microcrystalline cellulose Drugs 0.000 claims abstract description 9
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 9
- HPDKVTYVCYJOFZ-UHFFFAOYSA-N 2,2-dichloro-n,n-diethylethanamine Chemical compound CCN(CC)CC(Cl)Cl HPDKVTYVCYJOFZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 17
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 7
- 229920002678 cellulose Polymers 0.000 claims description 7
- 235000010980 cellulose Nutrition 0.000 claims description 7
- 239000001913 cellulose Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 230000005587 bubbling Effects 0.000 claims description 6
- 238000010000 carbonizing Methods 0.000 claims description 6
- 229920001519 homopolymer Polymers 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims description 4
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 230000007062 hydrolysis Effects 0.000 abstract description 8
- 230000005389 magnetism Effects 0.000 abstract description 6
- 239000006249 magnetic particle Substances 0.000 abstract description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 4
- 238000009830 intercalation Methods 0.000 abstract description 4
- 230000002687 intercalation Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 229920001046 Nanocellulose Polymers 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 239000004005 microsphere Substances 0.000 abstract description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229920003081 Povidone K 30 Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003808 methanol extraction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement 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
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B01J35/51—
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
Abstract
The present application relates to a magnetic solid acid catalyst and its application in catalyzing fructose hydrolysis reaction 3 O 4 Adding the nano particles into emulsion polymerization of microcrystalline cellulose (NCC) and hydroxyethyl methacrylate (HEM) to prepare magnetic composite microspheres; then introducing N atoms through the reaction of hydroxyl at the tail end of HEM polymer chain and dichloroethyl diethylamine; then, the nitrogen-containing magnetic NCC-g-HEM material and montmorillonite undergo an intercalation reaction to further protect magnetic particles, and finally, the magnetic solid acid catalyst is prepared through carbonization and sulfonation. The synthesized solid acid catalyst has higher magnetism and catalytic activity, the solid acid catalyst is coated by emulsion polymerization of nanocellulose and the intercalation reaction of montmorillonite reduces the influence of carbonization and sulfonation on internal magnetic particles, and the catalyst recovery rate is more than 90%; the prepared magnetic solid acid catalyst has better catalytic effect in the reaction of catalyzing the hydrolysis of fructose, and has higher yield and purity.
Description
Technical Field
The invention relates to the technical field of catalytic synthesis, in particular to a magnetic solid acid catalyst and application thereof in catalyzing fructose hydrolysis reaction.
Background
Organic compounds are ubiquitous in the various areas of the industry, while synthetic organic compounds are of great importance. More than half of the chemical products need to be used in the manufacturing process, and the successful development of a novel catalyst or a novel catalytic technology will bring great change to the whole chemical industry. Among the catalyst fields, acid catalysts are most widely used.
Compared with a liquid acid catalyst, the solid acid catalyst has the characteristics of stable property, easy recycling, small environmental pollution and the like. Although the solid acid catalyst can be simply filtered, separated and collected, the process is long and low-efficiency, and the magnetic material is introduced into the solid acid by adopting various methods to form the magnetic solid acid catalyst, so that the separation efficiency can be effectively improved. However, the surface activity and stability of the catalyst are relatively weakened due to stronger magnetism in the prior reported researches; and the original magnetic structure of the catalyst is often damaged in the sulfonation process, so that the balanced development of activity and magnetism is difficult to achieve.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a solid acid catalyst with relatively balanced surface catalytic activity and magnetism, which can effectively improve the reaction rate and the yield when being used for catalyzing the hydrolysis of fructose.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a magnetic solid acid is prepared by the following steps:
1) Weighing cellulose, and carrying out ultrasonic pretreatment in sulfuric acid solution to obtain microcrystalline cellulose, which is marked as NCC; dissolving a certain amount of sodium dodecyl benzene sulfonate in deionized water, and then weighing a certain amount of NCC and Fe 3 O 4 Dispersing the nano particles in water, heating to 70 ℃, stirring and bubbling nitrogen for 30min;
2) Under the protection of nitrogen, adding hydroxyethyl methacrylate into the step 1), dropwise adding 0.25mol/L ammonium persulfate aqueous solution, continuously stirring for reaction for 4 hours after the dropwise adding is finished, extracting with methanol to remove unreacted monomers and homopolymers, and drying to obtain magnetic NCC-g-HEM;
3) Mixing the magnetic NCC-g-HEM with dichloroethyldiethylamine, toluene and 20% sodium hydroxide solution according to the ratio of 1:1.2-2.0:10-30: adding 25-45 mass percent into a reaction bottle together, mixing uniformly, refluxing and stirring for 1h, carrying out suction filtration, washing 3-5 times by deionized water, and drying to obtain the nitrogen-containing magnetic NCC-g-HEM;
4) Dispersing montmorillonite powder in water, adding cetyl trimethyl ammonium bromide, performing ultrasonic treatment to uniformly disperse the montmorillonite powder, adding nitrogen-containing magnetic NCC-g-HEM and glutaraldehyde, performing ultrasonic treatment for 1h, and stirring for 3h at room temperature; standing for 12h after stirring, filtering to obtain a solid, washing with deionized water for 3-5 times, and drying to obtain a nitrogen-containing magnetic NCC-g-HEM/MMT composite material;
5) And (3) placing the nitrogen-containing magnetic NCC-g-HEM/MMT composite material in a tubular furnace for carbonization to obtain solid powder, cooling, sulfonating with concentrated sulfuric acid, filtering to obtain a solid, and drying in a vacuum oven to obtain the magnetic solid acid catalyst.
Further, the sodium dodecyl benzene sulfonate, NCC and Fe 3 O 4 The mass ratio of the nano particles to the hydroxyethyl methacrylate is 0.5:1:1-2:3-6, and the dosage of the ammonium persulfate is 1% of the mass of the hydroxyethyl methacrylate.
Further, the mass ratio of the montmorillonite powder to the hexadecyl trimethyl ammonium bromide to the nitrogen-containing magnetic NCC-g-HEM to the glutaraldehyde is 0.5-1:0.05:1:0.05.
Further, the carbonization condition in the step 5) is carbonization for 0.5h at 250-300 ℃ in nitrogen atmosphere; the sulfonation reaction condition is that the sulfonation is heated for 10 to 12 hours at the temperature of between 110 and 120 ℃.
The invention further provides an application of catalyzing fructose dehydration to generate 5-hydroxymethylfurfural by using the magnetic solid acid.
To prevent the magnetic particles from being adversely affected during subsequent carbonization and sulfonation, fe is added in the emulsion polymerization of nano-sized microcrystalline cellulose (NCC) and hydroxyethyl methacrylate (HEM) 3 O 4 Coating the magnetic composite microsphere by nano particles; then introducing N atoms through the reaction of hydroxyl groups at the tail end of the HEM polymer chain and dichloroethyldiethylamine, and increasing adsorption sites. The nitrogen-containing magnetic NCC-g-HEM material and montmorillonite are subjected to intercalation reaction to further protect magnetic particles, and meanwhile, the specific surface area of the composite material is increased under incomplete carbonization, so that the catalytic activity is improved.
The beneficial effects of the invention are as follows: the synthesized solid acid catalyst has higher magnetism and catalytic activity, the solid acid catalyst is coated by emulsion polymerization of nanocellulose and the intercalation reaction of montmorillonite reduces the influence of carbonization and sulfonation on internal magnetic particles, and the catalyst recovery rate is more than 90%; the prepared magnetic solid acid catalyst has better catalytic effect in the reaction of catalyzing the hydrolysis of fructose, and has higher yield and purity.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In addition, the technical features of the different embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The application provides a magnetic solid acid catalyst and application thereof in catalyzing dehydration of fructose to generate 5-hydroxymethylfurfural.
Example 1:
1. preparation of magnetic solid acid catalyst
1) Weighing cellulose, and carrying out ultrasonic pretreatment in sulfuric acid solution to obtain microcrystalline cellulose, which is marked as NCC; 5g of sodium dodecylbenzenesulfonate was dissolved in 200ml of deionized water, and then 10g of NCC and 10g of Fe were weighed out 3 O 4 Dispersing the nano particles in water, heating to 70 ℃, stirring and bubbling nitrogen for 30min;
2) Under the protection of nitrogen, adding 30g of hydroxyethyl methacrylate into the step 1), dropwise adding 5ml of 0.25mol/L ammonium persulfate aqueous solution, continuously stirring for reaction for 4 hours after the dropwise adding is finished, extracting with methanol to remove unreacted monomers and homopolymers, and drying to obtain magnetic NCC-g-HEM;
3) Adding the magnetic NCC-g-HEM, dichloroethyldiethylamine, toluene and 20% sodium hydroxide solution into a reaction bottle together according to the mass ratio of 1:1.2:10:25, mixing uniformly, refluxing and stirring for 1h, filtering, washing with deionized water for 3-5 times, and drying to obtain the nitrogen-containing magnetic NCC-g-HEM;
4) Dispersing 5g of montmorillonite powder in water, adding 0.5g of cetyltrimethylammonium bromide, carrying out ultrasonic treatment to uniformly disperse the montmorillonite powder, adding 10g of nitrogen-containing magnetic NCC-g-HEM and 0.5g of glutaraldehyde, continuing ultrasonic treatment for 1h, and stirring for 3h at room temperature; standing for 12h after stirring, filtering to obtain a solid, washing with deionized water for 3-5 times, and drying to obtain a nitrogen-containing magnetic NCC-g-HEM/MMT composite material;
5) And (3) placing the nitrogen-containing magnetic NCC-g-HEM/MMT composite material in a tubular furnace, carbonizing at 250 ℃ for 0.5h under nitrogen atmosphere to obtain solid powder, heating and sulfonating at 110 ℃ for 10h with concentrated sulfuric acid after cooling, filtering to obtain a solid, and drying in a vacuum oven to obtain the magnetic solid acid catalyst.
2. Catalytic fructose hydrolysis
Fructose, a magnetic solid acid catalyst and PVP K30 auxiliary agent are added into a reaction kettle according to a ratio of 10:4:3, and an appropriate amount of isopropanol is added as a solvent to react for 2 hours at 130 ℃, the mixture is placed into cold water to be cooled to room temperature at medium speed after the reaction is finished, the mixture is filtered, the composition of the reaction liquid is measured by high performance liquid chromatography, the fructose conversion rate and the yield and the selectivity of 5-hydroxymethylfurfural are calculated, and the results are recorded in table 1. The separated solid acid catalyst was used for the next batch reaction, and the percentage of catalytic activity to the first catalytic activity after 5 batches were used consecutively to demonstrate the stability of the catalyst, the closer to 100% the higher the stability.
Example 2:
1. preparation of magnetic solid acid catalyst
1) Weighing cellulose, and carrying out ultrasonic pretreatment in sulfuric acid solution to obtain microcrystalline cellulose, which is marked as NCC; 5g of sodium dodecylbenzenesulfonate was dissolved in 200ml of deionized water, and 10g of NCC and 15g of Fe were weighed out 3 O 4 Dispersing the nano particles in water, heating to 70 ℃, stirring and bubbling nitrogen for 30min;
2) Under the protection of nitrogen, adding 40g of hydroxyethyl methacrylate into the step 1), dropwise adding 5ml of 0.25mol/L ammonium persulfate aqueous solution, continuously stirring for reaction for 4 hours after the dropwise adding is finished, extracting with methanol to remove unreacted monomers and homopolymers, and drying to obtain magnetic NCC-g-HEM;
3) Adding the magnetic NCC-g-HEM, dichloroethyldiethylamine, toluene and 20% sodium hydroxide solution into a reaction bottle together according to the mass ratio of 1:1.5:15:30, mixing uniformly, refluxing and stirring for 1h, filtering, washing with deionized water for 3-5 times, and drying to obtain the nitrogen-containing magnetic NCC-g-HEM;
4) Dispersing 7g of montmorillonite powder in water, adding 0.5g of cetyltrimethylammonium bromide, carrying out ultrasonic treatment to uniformly disperse the montmorillonite powder, adding 10g of nitrogen-containing magnetic NCC-g-HEM and 0.5g of glutaraldehyde, continuing ultrasonic treatment for 1h, and stirring for 3h at room temperature; standing for 12h after stirring, filtering to obtain a solid, washing with deionized water for 3-5 times, and drying to obtain a nitrogen-containing magnetic NCC-g-HEM/MMT composite material;
5) And (3) placing the nitrogen-containing magnetic NCC-g-HEM/MMT composite material in a tubular furnace, carbonizing at 260 ℃ for 0.5h under nitrogen atmosphere to obtain solid powder, heating and sulfonating at 110 ℃ for 10h with concentrated sulfuric acid after cooling, filtering to obtain a solid, and drying in a vacuum oven to obtain the magnetic solid acid catalyst.
2. Catalytic fructose hydrolysis was as in example 1.
Example 3:
1. preparation of magnetic solid acid catalyst
1) Weighing cellulose, and carrying out ultrasonic pretreatment in sulfuric acid solution to obtain microcrystalline cellulose, which is marked as NCC; 5g of sodium dodecylbenzenesulfonate was dissolved in 200ml of deionized water, and 10g of NCC and 20g of Fe were weighed out 3 O 4 Dispersing the nano particles in water, heating to 70 ℃, stirring and bubbling nitrogen for 30min;
2) Under the protection of nitrogen, 50g of hydroxyethyl methacrylate is added into the step 1), 5ml of 0.25mol/L ammonium persulfate aqueous solution is dropwise added, stirring reaction is continued for 4 hours after the dropwise addition is completed, unreacted monomers and homopolymers are removed by methanol extraction, and the magnetic NCC-g-HEM is obtained by drying;
3) Adding the magnetic NCC-g-HEM, dichloroethyldiethylamine, toluene and 20% sodium hydroxide solution into a reaction bottle together according to the mass ratio of 1:1.5:15:30, mixing uniformly, refluxing and stirring for 1h, filtering, washing with deionized water for 3-5 times, and drying to obtain the nitrogen-containing magnetic NCC-g-HEM;
4) Dispersing 9g of montmorillonite powder in water, adding 0.5g of cetyltrimethylammonium bromide, carrying out ultrasonic treatment to uniformly disperse the montmorillonite powder, adding 10g of nitrogen-containing magnetic NCC-g-HEM and 0.5g of glutaraldehyde, continuing ultrasonic treatment for 1h, and stirring for 3h at room temperature; standing for 12h after stirring, filtering to obtain a solid, washing with deionized water for 3-5 times, and drying to obtain a nitrogen-containing magnetic NCC-g-HEM/MMT composite material;
5) And (3) placing the nitrogen-containing magnetic NCC-g-HEM/MMT composite material in a tubular furnace, carbonizing at 260 ℃ for 0.5h under nitrogen atmosphere to obtain solid powder, heating and sulfonating at 110 ℃ for 10h with concentrated sulfuric acid after cooling, filtering to obtain a solid, and drying in a vacuum oven to obtain the magnetic solid acid catalyst.
2. Catalytic fructose hydrolysis was as in example 1.
Example 4:
1. preparation of magnetic solid acid catalyst
1) Weighing cellulose, and carrying out ultrasonic pretreatment in sulfuric acid solution to obtain microcrystalline cellulose, which is marked as NCC; 5g of sodium dodecylbenzenesulfonate was dissolved in 200ml of deionized water, and 10g of NCC and 20g of Fe were weighed out 3 O 4 Dispersing the nano particles in water, and uniformly dispersing the nano particles by ultrasonic;
2) 5g of montmorillonite powder and 0.5g of cetyltrimethylammonium bromide are added into the step 1, ultrasonic treatment is carried out for 1h, and then stirring is carried out for 3h at room temperature; standing for 12h after stirring, filtering to obtain a solid, washing with deionized water for 3-5 times, and drying to obtain a magnetic NCC/MMT composite material;
3) And (3) placing the magnetic NCC/MMT composite material in a tube furnace, carbonizing at 260 ℃ for 0.5h under nitrogen atmosphere to obtain solid powder, heating and sulfonating at 110 ℃ for 10h with concentrated sulfuric acid after cooling, filtering to obtain a solid, and drying in a vacuum oven to obtain the magnetic solid acid catalyst.
2. Catalytic fructose hydrolysis was as in example 1.
Example 5:
1. preparation of magnetic solid acid catalyst
1) Weighing cellulose, and carrying out ultrasonic pretreatment in sulfuric acid solution to obtain microcrystalline cellulose, which is marked as NCC; 5g of sodium dodecylbenzenesulfonate was dissolved in 200ml of deionized water, and then 10g of NCC and 10g of Fe were weighed out 3 O 4 Dispersing the nano particles in water, heating to 70 ℃, stirring and bubbling nitrogen for 30min；
2) Under the protection of nitrogen, adding 30g of hydroxyethyl methacrylate into the step 1), dropwise adding 5ml of 0.25mol/L ammonium persulfate aqueous solution, continuously stirring for reaction for 4 hours after the dropwise adding is finished, extracting with methanol to remove unreacted monomers and homopolymers, and drying to obtain magnetic NCC-g-HEM;
3) Adding the magnetic NCC-g-HEM, dichloroethyldiethylamine, toluene and 20% sodium hydroxide solution into a reaction bottle together according to the mass ratio of 1:1.2:10:25, mixing uniformly, refluxing and stirring for 1h, filtering, washing with deionized water for 3-5 times, and drying to obtain the nitrogen-containing magnetic NCC-g-HEM;
4) And (3) placing the nitrogen-containing magnetic NCC-g-HEM in a tube furnace, carbonizing at 250 ℃ for 0.5h under nitrogen atmosphere to obtain solid powder, heating and sulfonating at 110 ℃ for 10h with concentrated sulfuric acid after cooling, filtering to obtain a solid, and drying in a vacuum oven to obtain the magnetic solid acid catalyst.
2. Catalytic fructose hydrolysis was as in example 1.
TABLE 1
In the above examples, NCC and Fe are used in example 4 3 O 4 The nano particles and montmorillonite powder are directly mixed, the magnetism is weakened in the carbonization process, the mixing compatibility of the three materials is poor, and the final stability is relatively weak. It can be seen from the table that examples 1 to 3 show excellent properties both in terms of stability and catalytic conversion to fructose and selectivity to the target product.
Although embodiments of the present invention have been disclosed above, it is not limited to the details and embodiments shown, it is well suited to various fields of use, and further modifications may be readily made by those skilled in the art without departing from the general concepts defined by the claims and the equivalents thereof, and therefore the invention is not limited to the specific details and examples shown and described herein.
Claims (4)
1. The magnetic solid acid catalyst is characterized by comprising the following preparation processes:
1) Weighing cellulose, and carrying out ultrasonic pretreatment in sulfuric acid solution to obtain microcrystalline cellulose, which is marked as NCC; dissolving a certain amount of sodium dodecyl benzene sulfonate in deionized water, and then weighing a certain amount of NCC and Fe 3 O 4 Dispersing the nano particles in water, heating to 70 ℃, stirring and bubbling nitrogen for 30min;
2) Under the protection of nitrogen, adding hydroxyethyl methacrylate into the step 1), dropwise adding 0.25mol/L ammonium persulfate aqueous solution, continuously stirring for reaction for 4 hours after the dropwise adding is finished, extracting with methanol to remove unreacted monomers and homopolymers, and drying to obtain magnetic NCC-g-HEM;
3) Mixing the magnetic NCC-g-HEM with dichloroethyldiethylamine, toluene and 20% sodium hydroxide solution according to the ratio of 1:1.2-2.0:10-30: adding 25-45 mass percent into a reaction bottle together, mixing uniformly, refluxing and stirring for 1h, carrying out suction filtration, washing 3-5 times by deionized water, and drying to obtain the nitrogen-containing magnetic NCC-g-HEM;
4) Dispersing montmorillonite powder in water, adding cetyl trimethyl ammonium bromide, performing ultrasonic treatment to uniformly disperse the montmorillonite powder, adding nitrogen-containing magnetic NCC-g-HEM and glutaraldehyde, performing ultrasonic treatment for 1h, and stirring for 3h at room temperature; standing for 12h after stirring, filtering to obtain a solid, washing with deionized water for 3-5 times, and drying to obtain a nitrogen-containing magnetic NCC-g-HEM/MMT composite material;
5) Carbonizing a nitrogen-containing magnetic NCC-g-HEM/MMT composite material in a tube furnace to obtain solid powder, cooling, sulfonating with concentrated sulfuric acid, filtering to obtain a solid, and drying in a vacuum oven to obtain a magnetic solid acid catalyst; wherein the carbonization condition is carbonization for 0.5h at 250-300 ℃ in nitrogen atmosphere; the sulfonation reaction condition is that the sulfonation is heated for 10 to 12 hours at the temperature of between 110 and 120 ℃.
2. The magnetic solid acid catalyst of claim 1, wherein the sodium dodecylbenzenesulfonate, NCC, and Fe 3 O 4 The mass ratio of the nano particles to the hydroxyethyl methacrylate is 0.5:1:1-2:3-6, and the ammonium persulfate is prepared from the following components by weight percentThe dosage is 1 to 2 percent of the mass of the hydroxyethyl methacrylate.
3. The magnetic solid acid catalyst according to claim 1, wherein the mass ratio of montmorillonite powder, cetyltrimethylammonium bromide, nitrogen-containing magnetic NCC-g-HEM and glutaraldehyde is 0.5-1:0.05:1:0.05.
4. Use of the magnetic solid acid catalyst of any one of claims 1-3 to catalyze dehydration of fructose to produce 5-hydroxymethylfurfural.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110996848.4A CN113663710B (en) | 2021-08-27 | 2021-08-27 | Magnetic solid acid catalyst and application thereof in catalyzing fructose hydrolysis reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110996848.4A CN113663710B (en) | 2021-08-27 | 2021-08-27 | Magnetic solid acid catalyst and application thereof in catalyzing fructose hydrolysis reaction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113663710A CN113663710A (en) | 2021-11-19 |
| CN113663710B true CN113663710B (en) | 2023-10-27 |
Family
ID=78547063
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110996848.4A Active CN113663710B (en) | 2021-08-27 | 2021-08-27 | Magnetic solid acid catalyst and application thereof in catalyzing fructose hydrolysis reaction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113663710B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114602505B (en) * | 2022-03-16 | 2023-04-25 | 重庆工商大学 | Magnetic carbon-based solid acid catalyst, preparation method thereof, application thereof in sludge treatment and method for recycling nitrogen and phosphorus by hydrothermal carbonization |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070864A (en) * | 2010-12-18 | 2011-05-25 | 四川大学 | Nanoscale polymethylmethacrylate magnetic composite microsphere and preparation method thereof |
| CN103567359A (en) * | 2013-10-11 | 2014-02-12 | 铜陵市经纬流体科技有限公司 | Clay green sand for high-pressure molding and preparation method thereof |
| CN104624207A (en) * | 2015-01-15 | 2015-05-20 | 淮阴师范学院 | Preparation method of xylogen-based magnetic solid acid catalyst |
| CN105195111A (en) * | 2015-10-26 | 2015-12-30 | 福建农林大学 | Preparation method of polyethylenimine modified chitosan-coated magnetic nanocellulose adsorbent and product thereof |
| CN106040194A (en) * | 2016-06-23 | 2016-10-26 | 南京师范大学 | Chitosan magnetic composite spherule adsorbent with core-brush structure as well as preparation method and application thereof |
| CN106215951A (en) * | 2016-07-29 | 2016-12-14 | 中国科学院广州能源研究所 | A kind of core-shell structure magnetic carbon-based solid acid catalyst and preparation method thereof and the application during lignocellulose hydrolysis and saccharification |
| WO2017060311A1 (en) * | 2015-10-05 | 2017-04-13 | Universidad Del País Vasco/Euskal Herriko Unibertsitatea | Method for preparing composite particles comprising a magnetic core and a photocatalytically active coating, and composite particles obtainable by said method |
| CN108299651A (en) * | 2018-02-09 | 2018-07-20 | 西南民族大学 | A kind of intelligent nano chiral selector material and its preparation and application |
| CN109621977A (en) * | 2018-12-17 | 2019-04-16 | 陕西科技大学 | A kind of magnetism carbonaceous solid acid catalyst and preparation method thereof and preparing the application in levulinate |
| WO2020006648A1 (en) * | 2018-07-05 | 2020-01-09 | X'aan Innovations Inc. | Ammonium polyphosphate based and diammonium phosphate based fire-retardant compositions |
-
2021
- 2021-08-27 CN CN202110996848.4A patent/CN113663710B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070864A (en) * | 2010-12-18 | 2011-05-25 | 四川大学 | Nanoscale polymethylmethacrylate magnetic composite microsphere and preparation method thereof |
| CN103567359A (en) * | 2013-10-11 | 2014-02-12 | 铜陵市经纬流体科技有限公司 | Clay green sand for high-pressure molding and preparation method thereof |
| CN104624207A (en) * | 2015-01-15 | 2015-05-20 | 淮阴师范学院 | Preparation method of xylogen-based magnetic solid acid catalyst |
| WO2017060311A1 (en) * | 2015-10-05 | 2017-04-13 | Universidad Del País Vasco/Euskal Herriko Unibertsitatea | Method for preparing composite particles comprising a magnetic core and a photocatalytically active coating, and composite particles obtainable by said method |
| CN105195111A (en) * | 2015-10-26 | 2015-12-30 | 福建农林大学 | Preparation method of polyethylenimine modified chitosan-coated magnetic nanocellulose adsorbent and product thereof |
| CN106040194A (en) * | 2016-06-23 | 2016-10-26 | 南京师范大学 | Chitosan magnetic composite spherule adsorbent with core-brush structure as well as preparation method and application thereof |
| CN106215951A (en) * | 2016-07-29 | 2016-12-14 | 中国科学院广州能源研究所 | A kind of core-shell structure magnetic carbon-based solid acid catalyst and preparation method thereof and the application during lignocellulose hydrolysis and saccharification |
| CN108299651A (en) * | 2018-02-09 | 2018-07-20 | 西南民族大学 | A kind of intelligent nano chiral selector material and its preparation and application |
| WO2020006648A1 (en) * | 2018-07-05 | 2020-01-09 | X'aan Innovations Inc. | Ammonium polyphosphate based and diammonium phosphate based fire-retardant compositions |
| CN109621977A (en) * | 2018-12-17 | 2019-04-16 | 陕西科技大学 | A kind of magnetism carbonaceous solid acid catalyst and preparation method thereof and preparing the application in levulinate |
Non-Patent Citations (4)
| Title |
|---|
| "Magnetic natural composite Fe3O4-chitosan@bentonite for removal of heavy metals from acid mine drainage";Guorui Feng et al.;《Journal of Colloid and Interface Science》;第538卷;第132页摘要，第133页2.2节，第134页3.1节第5段，第136页Fig. 4. * |
| "Synthesis of montmorillonite/Fe3O4-OTAB composite capable of using as anisotropic nanoparticles";Hua Chen et al.;《Applied Surface Science》;第402卷;384-391 * |
| "磁性碳质材料催化糖类制备5-羟甲基糠醛和5-乙氧基甲基糠醛的研究";姚远;《应用化工》;第45卷(第07期);1258-1261+1266 * |
| 张玉龙.《纳米复合材料手册》.中国石化出版社,2005,第229页3.4.1.1节. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113663710A (en) | 2021-11-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104248987B (en) | The preparation method of spherical montmorillonite mesoporous composite material and loaded catalyst and its preparation method and application and ethyl acetate | |
| CN113663710B (en) | Magnetic solid acid catalyst and application thereof in catalyzing fructose hydrolysis reaction | |
| CN110540210B (en) | Low-energy-consumption large-pore-volume silica gel and production method thereof | |
| CN104248993A (en) | Spherical diatomite mesoporous composite and supported catalyst, preparation method thereof and application thereof, and ethyl acetate preparation method | |
| CN104248984B (en) | The preparation method of spherical diatomite mesoporous composite material and loaded catalyst and its preparation method and application and ethyl acetate | |
| CN102634015A (en) | Synthesis method of poly(m-phenylenediamine) nanoparticles | |
| CN102935381A (en) | Amphiphilic type rare earth polyacid catalytic material and preparation method and application thereof | |
| CN113289692A (en) | Magnetic biomass solid catalyst and preparation and application thereof | |
| CN112058236A (en) | Preparation of ferrocenyl metal-organic framework microspheres and application of ferrocenyl metal-organic framework microspheres in gold recovery | |
| CN113860417B (en) | Industrial wastewater treatment agent and preparation method thereof | |
| CN107245136B (en) | A kind of ordered mesoporous polymer material and its preparation method and application | |
| CN113019325B (en) | Magnetic adsorption material and preparation method thereof | |
| CN113429534B (en) | Preparation method of high-stability strong-basicity porous ion exchange material | |
| CN113603580A (en) | Method for synthesizing methacrylic acid by decarboxylation of itaconic acid | |
| CN113845880A (en) | Silver nanowire @ polypyrrole-ferroferric oxide composite wave-absorbing material and preparation method thereof | |
| CN111974409A (en) | Flaky porous manganese-doped nickel oxide catalyst, preparation method and application thereof | |
| CN111961015A (en) | Method for preparing 2, 5-furandimethanol by catalyzing 5-hydroxymethylfurfural | |
| CN111944083A (en) | Preparation method of modified macroporous acidic cation exchange resin | |
| CN111790441A (en) | Polyaniline loaded copper-iron catalyst material and preparation method and application thereof | |
| CN114011471B (en) | MnCO 3 Modified catalyst @ ZIF-8, preparation method and application | |
| CN103864550A (en) | Application of gold-nickel alloy catalyst in selective hydrogenation of aromatic nitro compound | |
| CN113754506B (en) | Nano core-shell combustion catalyst and preparation method thereof | |
| CN113582948B (en) | Caffeic acid based triglycidyl ester and preparation method and application thereof | |
| CN112447353B (en) | Corrosion-resistant magnetic material and production process thereof | |
| CN107715917A (en) | Phosphoric acid sexual intercourse linked polymer supported palladium nanocatalyst and preparation and application |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |