CN113663710A - 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
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- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 239000011973 solid acid Substances 0.000 title claims abstract description 36
- 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
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 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 17
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 17
- 239000002131 composite material Substances 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 15
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims abstract description 14
- 239000002105 nanoparticle Substances 0.000 claims abstract description 13
- 238000003763 carbonization Methods 0.000 claims abstract description 10
- 229920002678 cellulose Polymers 0.000 claims abstract description 10
- 239000001913 cellulose Substances 0.000 claims abstract description 10
- 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
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 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
- 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
- 238000001914 filtration Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 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
- 238000001816 cooling Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 7
- 235000010980 cellulose Nutrition 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
- 229920001519 homopolymer Polymers 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000000967 suction filtration 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
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 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
- 239000004005 microsphere Substances 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 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
- 238000010000 carbonizing Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 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
- 239000000047 product Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 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
- 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
- 239000000706 filtrate Substances 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification 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 scheme relates to a magnetic solid acid catalyst and application thereof in catalyzing fructose hydrolysis reaction, and Fe3O4Adding the nano particles into the emulsion polymerization of microcrystalline cellulose (NCC) and hydroxyethyl methacrylate (HEM) to prepare magnetic composite microspheres; then leading N atoms by reacting hydroxyl at the tail end of a HEM polymer chain with dichloroethyl diethylamine; then the nitrogen-containing magnetic NCC-g-HEM material and montmorillonite are subjected to intercalation reaction to further protect magnetic particles, and finally the magnetic solid acid catalyst is prepared through carbonization and sulfonation. The solid acid catalyst synthesized by the scheme has higher magnetism and catalytic activity, is coated by emulsion polymerization of nano-cellulose, and contains montmorilloniteThe intercalation reaction reduces the influence of carbonization and sulfonation on the internal magnetic particles, and the recovery rate of the catalyst is more than 90 percent; the prepared magnetic solid acid catalyst has a good catalytic effect when used for catalyzing the reaction of fructose hydrolysis, and has high 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 have no place in the fields of various industries, and artificially synthesized organic compounds occupy an important position. More than half of the manufacturing process of chemical products needs to use catalysts, and the successful development of a novel catalyst or a novel catalytic technology can bring important changes to the whole chemical industry. In the field of catalysts, acid catalysts are most widely used.
Compared with a liquid acid catalyst, the solid acid catalyst has the characteristics of stable property, easy reutilization, small environmental pollution and the like. Although the solid acid catalyst can be collected by simple filtration and separation, the process is long and inefficient, and the magnetic material is introduced into the solid acid by 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 existing reported research; and the original magnetic structure of the catalyst is often destroyed in the sulfonation process, and 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 the solid acid catalyst with relatively balanced surface catalytic activity and magnetism, which can effectively improve the reaction rate and yield when used for catalyzing fructose hydrolysis.
In order to achieve the purpose, the invention provides the following technical scheme:
a magnetic solid acid is prepared by the following steps:
1) weighing cellulose, and performing ultrasonic pretreatment in a sulfuric acid solution to obtain microcrystalline cellulose, which is recorded as NCC; dissolving a certain amount of sodium dodecyl benzene sulfonate in deionized water, and then weighing a certain amount of NCC and Fe3O4Dispersing the nano particles in water, heating to 70 ℃, stirring, and introducing nitrogen for bubbling for 30 min;
2) under the protection of nitrogen, adding hydroxyethyl methacrylate into the step 1), dropwise adding 0.25mol/L ammonium persulfate aqueous solution, continuing stirring and reacting for 4 hours after dropwise adding is finished, extracting by using methanol to remove unreacted monomers and homopolymers, and drying to obtain magnetic NCC-g-HEM;
3) mixing the magnetic NCC-g-HEM with dichloroethyl diethylamine, toluene and 20% sodium hydroxide solution according to the weight ratio of 1: 1.2-2.0: 10-30: adding the mixture into a reaction bottle together in a mass ratio of 25-45, uniformly mixing, refluxing and stirring for 1h, performing suction filtration, washing with deionized water for 3-5 times, and drying to obtain 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, continuing ultrasonic treatment for 1h, and then stirring at room temperature for 3 h; stirring, standing for 12h, filtering to obtain a solid, washing with deionized water for 3-5 times, and drying to obtain the nitrogen-containing magnetic NCC-g-HEM/MMT composite material;
5) and (2) putting the nitrogen-containing magnetic NCC-g-HEM/MMT composite material into a tubular furnace for carbonization to obtain solid powder, cooling, sulfonating by concentrated sulfuric acid, filtering to obtain a solid, and drying in a vacuum oven to obtain the magnetic solid acid catalyst.
Further, the sodium dodecylbenzene sulfonate, NCC and Fe3O4The mass ratio of the nanoparticles to the hydroxyethyl methacrylate is 0.5:1: 1-2: 3-6, and the amount of the ammonium persulfate is 1% of the mass of the hydroxyethyl methacrylate.
Further, the mass ratio of the montmorillonite powder, the hexadecyl trimethyl ammonium bromide, the nitrogen-containing magnetic NCC-g-HEM and the glutaraldehyde is 0.5-1: 0.05:1: 0.05.
Further, in the step 5), carbonizing for 0.5h at 250-300 ℃ in a nitrogen atmosphere; the sulfonation reaction condition is heating sulfonation for 10-12 h at 110-120 ℃.
The invention further provides an application of the magnetic solid acid in catalyzing fructose dehydration to generate 5-hydroxymethylfurfural.
In order to prevent the magnetic particles from being adversely affected in the subsequent carbonization and sulfonation processes, Fe is added in the emulsion polymerization of nano microcrystalline cellulose (NCC) and hydroxyethyl methacrylate (HEM)3O4Coating the magnetic composite microspheres with nanoparticles to obtain magnetic composite microspheres; then N atoms are introduced by the reaction of hydroxyl at the end of the HEM polymer chain with dichloroethyl diethylamine to increase 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 improved under the condition of incomplete carbonization, so that the catalytic activity is improved.
The invention has the beneficial effects that: the synthesized solid acid catalyst has higher magnetism and catalytic activity, the nano-cellulose is coated by emulsion polymerization of the nano-cellulose, and the influence of carbonization and sulfonation on internal magnetic particles is reduced by intercalation reaction of montmorillonite, and the recovery rate of the catalyst is more than 90 percent; the prepared magnetic solid acid catalyst has a good catalytic effect when used for catalyzing the reaction of fructose hydrolysis, and has high yield and purity.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The scheme provides a magnetic solid acid catalyst and application thereof in catalyzing fructose dehydration to generate 5-hydroxymethylfurfural.
Example 1:
preparation of magnetic solid acid catalyst
1) Weighing cellulose, and performing ultrasonic pretreatment in a sulfuric acid solution to obtain microcrystalline cellulose, which is recorded as NCC; 5g of sodium dodecylbenzenesulfonate was dissolved in 200ml of deionized water, and then 10g of NCC and 10g of Fe were weighed3O4Dispersing the nano particles in water, heating to 70 ℃, stirring, and introducing nitrogen for bubbling for 30 min;
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, continuing stirring and reacting for 4 hours after dropwise adding is finished, extracting by using methanol to remove unreacted monomers and homopolymers, and drying to obtain magnetic NCC-g-HEM;
3) adding the magnetic NCC-g-HEM, dichloroethyl diethylamine, toluene and 20% sodium hydroxide solution into a reaction bottle according to the mass ratio of 1:1.2:10:25, uniformly mixing, refluxing and stirring for 1h, performing suction filtration, washing for 3-5 times by using deionized water, and drying to obtain nitrogen-containing magnetic NCC-g-HEM;
4) dispersing 5g of montmorillonite powder in water, adding 0.5g of hexadecyl trimethyl ammonium bromide, performing 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 then stirring at room temperature for 3 h; stirring, standing for 12h, filtering to obtain a solid, washing with deionized water for 3-5 times, and drying to obtain the nitrogen-containing magnetic NCC-g-HEM/MMT composite material;
5) putting the nitrogen-containing magnetic NCC-g-HEM/MMT composite material into a tubular furnace, carbonizing at 250 ℃ for 0.5h under the nitrogen atmosphere to obtain solid powder, cooling, heating and sulfonating at 110 ℃ for 10h by using concentrated sulfuric acid, filtering to obtain a solid, and drying in a vacuum oven to obtain the magnetic solid acid catalyst.
Secondly, catalyzing fructose hydrolysis
Adding fructose, a magnetic solid acid catalyst and a PVP K30 auxiliary agent into a reaction kettle according to the ratio of 10:4:3, adding a proper amount of isopropanol as a solvent, reacting for 2 hours at 130 ℃, placing the mixture into cold water after the reaction is finished, quickly cooling the mixture to room temperature, filtering, taking filtrate, measuring the composition of the reaction solution by using a high performance liquid chromatography, calculating the conversion rate of the fructose and the yield and selectivity of 5-hydroxymethylfurfural, and recording the results in Table 1. The separated solid acid catalyst is used for the next batch reaction, the percentage of the catalytic activity to the first catalytic activity after continuously using 5 batches is used for explaining the stability of the catalyst, and the closer to 100 percent, the higher the stability is.
Example 2:
preparation of magnetic solid acid catalyst
1) Weighing cellulose, and performing ultrasonic pretreatment in a sulfuric acid solution to obtain microcrystalline cellulose, which is recorded as NCC; 5g of sodium dodecylbenzenesulfonate was dissolved in 200ml of deionized water, and then 10g of NCC and 15g of Fe were weighed3O4Dispersing the nano particles in water, heating to 70 ℃, stirring, and introducing nitrogen for bubbling for 30 min;
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, continuing stirring and reacting for 4 hours after dropwise adding is finished, extracting by using methanol to remove unreacted monomers and homopolymers, and drying to obtain magnetic NCC-g-HEM;
3) adding the magnetic NCC-g-HEM, dichloroethyl diethylamine, toluene and 20% sodium hydroxide solution into a reaction bottle according to the mass ratio of 1:1.5:15:30, uniformly mixing, refluxing and stirring for 1h, performing suction filtration, washing for 3-5 times by using deionized water, and drying to obtain nitrogen-containing magnetic NCC-g-HEM;
4) dispersing 7g of montmorillonite powder in water, adding 0.5g of hexadecyl trimethyl ammonium bromide, performing 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 then stirring at room temperature for 3 h; stirring, standing for 12h, filtering to obtain a solid, washing with deionized water for 3-5 times, and drying to obtain the nitrogen-containing magnetic NCC-g-HEM/MMT composite material;
5) putting the nitrogen-containing magnetic NCC-g-HEM/MMT composite material into a tubular furnace, carbonizing at 260 ℃ for 0.5h under the nitrogen atmosphere to obtain solid powder, cooling, heating and sulfonating at 110 ℃ for 10h by using concentrated sulfuric acid, filtering to obtain a solid, and drying in a vacuum oven to obtain the magnetic solid acid catalyst.
Secondly, fructose hydrolysis is catalyzed as in example 1.
Example 3:
preparation of magnetic solid acid catalyst
1) Weighing cellulose, and performing ultrasonic pretreatment in a sulfuric acid solution to obtain microcrystalline cellulose, which is recorded as NCC; 5g of sodium dodecylbenzenesulfonate was dissolved in 200ml of deionized water, and then 10g of NCC and 20g of Fe were weighed3O4Dispersing the nano particles in water, heating to 70 ℃, stirring, and introducing nitrogen for bubbling for 30 min;
2) under the protection of nitrogen, adding 50g of hydroxyethyl methacrylate into the step 1), dropwise adding 5ml of 0.25mol/L ammonium persulfate aqueous solution, continuously stirring and reacting for 4 hours after dropwise adding is finished, extracting by using methanol to remove unreacted monomers and homopolymers, and drying to obtain magnetic NCC-g-HEM;
3) adding the magnetic NCC-g-HEM, dichloroethyl diethylamine, toluene and 20% sodium hydroxide solution into a reaction bottle according to the mass ratio of 1:1.5:15:30, uniformly mixing, refluxing and stirring for 1h, performing suction filtration, washing for 3-5 times by using deionized water, and drying to obtain nitrogen-containing magnetic NCC-g-HEM;
4) dispersing 9g of montmorillonite powder in water, adding 0.5g of hexadecyl trimethyl ammonium bromide, performing 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 then stirring at room temperature for 3 h; stirring, standing for 12h, filtering to obtain a solid, washing with deionized water for 3-5 times, and drying to obtain the nitrogen-containing magnetic NCC-g-HEM/MMT composite material;
5) putting the nitrogen-containing magnetic NCC-g-HEM/MMT composite material into a tubular furnace, carbonizing at 260 ℃ for 0.5h under the nitrogen atmosphere to obtain solid powder, cooling, heating and sulfonating at 110 ℃ for 10h by using concentrated sulfuric acid, filtering to obtain a solid, and drying in a vacuum oven to obtain the magnetic solid acid catalyst.
Secondly, fructose hydrolysis is catalyzed as in example 1.
Example 4:
preparation of magnetic solid acid catalyst
1) Weighing cellulose, and performing ultrasonic pretreatment in a sulfuric acid solution to obtain microcrystalline cellulose, which is recorded as NCC; 5g of sodium dodecylbenzenesulfonate was dissolved in 200ml of deionized water, and then 10g of NCC and 20g of Fe were weighed3O4Dispersing the nano particles in water, and performing ultrasonic treatment to uniformly disperse the nano particles;
2) adding 5g of montmorillonite powder and 0.5g of hexadecyl trimethyl ammonium bromide into the mixture obtained in the step 1, carrying out ultrasonic treatment for 1 hour, and then stirring for 3 hours at room temperature; stirring, standing for 12h, filtering to obtain a solid, washing with deionized water for 3-5 times, and drying to obtain a magnetic NCC/MMT composite material;
3) placing the magnetic NCC/MMT composite material in a tubular furnace, carbonizing at 260 ℃ for 0.5h under the nitrogen atmosphere to obtain solid powder, cooling, heating and sulfonating at 110 ℃ for 10h by using concentrated sulfuric acid, filtering to obtain a solid, and drying in a vacuum oven to obtain the magnetic solid acid catalyst.
Secondly, fructose hydrolysis is catalyzed as in example 1.
Example 5:
preparation of magnetic solid acid catalyst
1) Weighing cellulose, and performing ultrasonic pretreatment in a sulfuric acid solution to obtain microcrystalline cellulose, which is recorded as NCC; 5g of sodium dodecylbenzenesulfonate was dissolved in 200ml of deionized water, and then 10g of NCC and 10g of Fe were weighed3O4Dispersing the nano particles in water, heating to 70 ℃, stirring, and introducing nitrogen for bubbling for 30 min;
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, continuing stirring and reacting for 4 hours after dropwise adding is finished, extracting by using methanol to remove unreacted monomers and homopolymers, and drying to obtain magnetic NCC-g-HEM;
3) adding the magnetic NCC-g-HEM, dichloroethyl diethylamine, toluene and 20% sodium hydroxide solution into a reaction bottle according to the mass ratio of 1:1.2:10:25, uniformly mixing, refluxing and stirring for 1h, performing suction filtration, washing for 3-5 times by using deionized water, and drying to obtain nitrogen-containing magnetic NCC-g-HEM;
4) and (2) putting the nitrogen-containing magnetic NCC-g-HEM into a tubular furnace, carbonizing at 250 ℃ for 0.5h in the nitrogen atmosphere to obtain solid powder, cooling, heating and sulfonating at 110 ℃ for 10h by using concentrated sulfuric acid, filtering to obtain a solid, and drying in a vacuum oven to obtain the magnetic solid acid catalyst.
Secondly, fructose hydrolysis is catalyzed as in example 1.
TABLE 1
In the above examples, NCC and Fe were used in example 43O4The nano particles and the montmorillonite powder are directly mixed, the magnetism is weakened in the carbonization process, the compatibility of the three materials is poor, and the final stability is relatively weak. It can be seen from the table that examples 1-3 show excellent performance in both stability and catalytic conversion of fructose and selectivity to the desired product.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details and examples shown and described herein, without departing from the general concept defined by the claims and their equivalents.
Claims (5)
1. The magnetic solid acid catalyst is characterized by being prepared by the following steps:
1) weighing cellulose, and performing ultrasonic pretreatment in a sulfuric acid solution to obtain microcrystalline cellulose, which is recorded as NCC; dissolving a certain amount of sodium dodecyl benzene sulfonate in deionized water, and then weighing a certain amount of NCC and Fe3O4Dispersing the nano particles in water, heating to 70 ℃, stirring, and introducing nitrogen for bubbling for 30 min;
2) under the protection of nitrogen, adding hydroxyethyl methacrylate into the step 1), dropwise adding 0.25mol/L ammonium persulfate aqueous solution, continuing stirring and reacting for 4 hours after dropwise adding is finished, extracting by using methanol to remove unreacted monomers and homopolymers, and drying to obtain magnetic NCC-g-HEM;
3) mixing the magnetic NCC-g-HEM with dichloroethyl diethylamine, toluene and 20% sodium hydroxide solution according to the weight ratio of 1: 1.2-2.0: 10-30: adding the mixture into a reaction bottle together in a mass ratio of 25-45, uniformly mixing, refluxing and stirring for 1h, performing suction filtration, washing with deionized water for 3-5 times, and drying to obtain 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, continuing ultrasonic treatment for 1h, and then stirring at room temperature for 3 h; stirring, standing for 12h, filtering to obtain a solid, washing with deionized water for 3-5 times, and drying to obtain the nitrogen-containing magnetic NCC-g-HEM/MMT composite material;
5) and (2) putting the nitrogen-containing magnetic NCC-g-HEM/MMT composite material into a tubular furnace for carbonization to obtain solid powder, cooling, sulfonating by concentrated sulfuric acid, filtering to obtain a solid, and drying in a vacuum oven to obtain the magnetic solid acid catalyst.
2. The magnetic solid acid catalyst of claim 1, wherein the sodium dodecylbenzenesulfonate, NCC and Fe3O4The mass ratio of the nano particles to the hydroxyethyl methacrylate is 0.5:1: 1-2: 3-6, and the amount of the ammonium persulfate is 1-2% of the mass of the hydroxyethyl methacrylate.
3. The magnetic solid acid catalyst according to claim 1, wherein the mass ratio of the montmorillonite powder, the cetyltrimethylammonium bromide, the nitrogen-containing magnetic NCC-g-HEM and the glutaraldehyde is 0.5-1: 0.05:1: 0.05.
4. The magnetic solid acid catalyst according to claim 1, wherein the carbonization condition in the step 5) is carbonization at 250-300 ℃ for 0.5h in a nitrogen atmosphere; the sulfonation reaction condition is heating sulfonation for 10-12 h at 110-120 ℃.
5. Use of the magnetic solid acid catalyst of any one of claims 1-4 to catalyze the dehydration of fructose to 5-hydroxymethylfurfural.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114602505A (en) * | 2022-03-16 | 2022-06-10 | 重庆工商大学 | Magnetic carbon-based solid acid catalyst, preparation method thereof, application of magnetic carbon-based solid acid catalyst in sludge treatment, and method for recovering nitrogen and phosphorus through 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 (3)
| Title |
|---|
| GUORUI FENG ET AL.: ""Magnetic natural composite Fe3O4-chitosan@bentonite for removal of heavy metals from acid mine drainage"", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》, vol. 538, pages 132 * |
| HUA CHEN ET AL.: ""Synthesis of montmorillonite/Fe3O4-OTAB composite capable of using as anisotropic nanoparticles"", 《APPLIED SURFACE SCIENCE》, vol. 402, pages 384 - 391 * |
| 姚远: ""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"", 《应用化工》, vol. 45, no. 07, pages 1258 - 1261 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114602505A (en) * | 2022-03-16 | 2022-06-10 | 重庆工商大学 | Magnetic carbon-based solid acid catalyst, preparation method thereof, application of magnetic carbon-based solid acid catalyst in sludge treatment, and method for recovering nitrogen and phosphorus through hydrothermal carbonization |
| 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 |
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