CN109433264A - A kind of preparation method of silica and graphene oxide enhancing copper alginate aerosol catalytic agent - Google Patents
A kind of preparation method of silica and graphene oxide enhancing copper alginate aerosol catalytic agent Download PDFInfo
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- CN109433264A CN109433264A CN201811478404.6A CN201811478404A CN109433264A CN 109433264 A CN109433264 A CN 109433264A CN 201811478404 A CN201811478404 A CN 201811478404A CN 109433264 A CN109433264 A CN 109433264A
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- graphene oxide
- aerosol
- alginate
- catalytic agent
- silica
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 235000010443 alginic acid Nutrition 0.000 title claims abstract description 32
- 229920000615 alginic acid Polymers 0.000 title claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229940072056 alginate Drugs 0.000 title claims abstract description 30
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 29
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 28
- 239000010949 copper Substances 0.000 title claims abstract description 28
- 239000000443 aerosol Substances 0.000 title claims abstract description 26
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 15
- 230000002708 enhancing effect Effects 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000012153 distilled water Substances 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000661 sodium alginate Substances 0.000 claims abstract description 5
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 5
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 5
- 238000002604 ultrasonography Methods 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 20
- 235000019441 ethanol Nutrition 0.000 claims description 12
- 239000000017 hydrogel Substances 0.000 claims description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000011010 flushing procedure Methods 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims 3
- 239000012266 salt solution Substances 0.000 claims 3
- 150000001879 copper Chemical class 0.000 claims 2
- 239000008236 heating water Substances 0.000 claims 1
- 229910021645 metal ion Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- 230000002787 reinforcement Effects 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 description 37
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 36
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 28
- 239000012429 reaction media Substances 0.000 description 11
- 238000003760 magnetic stirring Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 229920001282 polysaccharide Polymers 0.000 description 5
- 239000005017 polysaccharide Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 150000004804 polysaccharides Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000000783 alginic acid Substances 0.000 description 2
- 229960001126 alginic acid Drugs 0.000 description 2
- 150000004781 alginic acids Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000033444 hydroxylation Effects 0.000 description 2
- 238000005805 hydroxylation reaction Methods 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- AEMOLEFTQBMNLQ-AZLKCVHYSA-N (2r,3s,4s,5s,6r)-3,4,5,6-tetrahydroxyoxane-2-carboxylic acid Chemical compound O[C@@H]1O[C@@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H]1O AEMOLEFTQBMNLQ-AZLKCVHYSA-N 0.000 description 1
- AEMOLEFTQBMNLQ-SYJWYVCOSA-N (2s,3s,4s,5s,6r)-3,4,5,6-tetrahydroxyoxane-2-carboxylic acid Chemical compound O[C@@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H]1O AEMOLEFTQBMNLQ-SYJWYVCOSA-N 0.000 description 1
- 241001474374 Blennius Species 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 206010067482 No adverse event Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- RRTCFFFUTAGOSG-UHFFFAOYSA-N benzene;phenol Chemical compound C1=CC=CC=C1.OC1=CC=CC=C1 RRTCFFFUTAGOSG-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- -1 polysaccharide alginate Chemical class 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000009941 weaving 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/58—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of molecular oxygen
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4288—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using O nucleophiles, e.g. alcohols, carboxylates, esters
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention discloses the preparation method of a kind of silica and graphene oxide enhancing copper alginate aerosol catalytic agent, introduces inorganic reinforcement silica and graphene oxide increases the mechanical performance of metal copper alginate aerosol.It include: that graphene oxide is added in distilled water, ultrasound adds sodium alginate and introduce silica, add water dispenser tool to be stirred until homogeneous thick, gained viscous liquid is instilled mold, is immersed in isothermal reaction in metal copper solution to being uniformly dispersed.It is freeze-dried later to get finished product.The mechanical performance of copper alginate aerosol catalytic agent prepared by the present invention greatly improves.
Description
Technical field
The present invention relates to the preparation methods of a kind of silica and graphene oxide enhancing copper alginate aerosol catalytic agent.
Background technique
Alginate is widely used in the products such as food, medicine, weaving, printing and dyeing, papermaking, daily-use chemical industry, as thickener,
Emulsifier, stabilizer, adhesive, sizing agent etc..
Alginate is the high-molecular compound extracted from brown alga, is by beta-D-mannuronic acid (M unit) and α-L-
Guluronic acid (G unit) relies on Isosorbide-5-Nitrae-glucosides key connection, and the linear polysaccharide being made of different GGG, MMM segments.It
It is that unique one kind can be dissolved in water at room temperature and form the polysaccharide of the hydrosol, line style long chain is similar to pure polyuronide
Strand.
Natural polysaccharide alginate becomes metallic catalyst carrier for the good adsorption properties of metal for it and provides item
Part.Meanwhile metal alginate aerosol specific surface area with higher, it can effectively overcome the hydrosol and xerogel non-porous
The deficiency low with specific surface area increases catalytic reaction activity.However, the mechanical performance of alginate aerosol catalytic agent, especially
It is that compression strength is relatively low, which greatly limits its applications in terms of Industrial Catalysis field and transport storage.
Graphene is the material that current nature is most thin, most tough, and than taller 200 times of steel, it has breaking strength
There are the characteristics such as extraordinary thermal conductivity, electrical conductance, translucency and extra specific surface area, while there is preferable elasticity.It is unique
Structure and performance be remarkably improved the mechanical performance and thermal stability of composite material.Graphene oxide is a kind of heavy of graphene
Derivative is wanted, there are a large amount of hydroxyl, epoxy group and carboxyl in surface, there is good dispersibility in aqueous solution and polar solvent,
Nanometer composite hydrogel material can be formed with hydrophilic polymer.The hydrophilic radical of graphene oxide enhances graphene oxide
Interfacial interaction between basis material has good compatibility, can significantly improve the mechanical property of material.In recent years,
Graphene is widely used in the reinforcing material of functional material, scientific research personnel's discovery, and a small amount of graphene that adds can effectively increase
Add the mechanical strength of functional material.
Silica as compound phase it is most widely used be silica nanoparticle.Nano silica in cotton-shaped or
Reticular structure has the distinctive small-size effect of nanoparticle and skin effect.Silica is evenly distributed on nano-scale
In organic matter reticular structure, since its higher surface can be combined with the surface energy, easily tied on a molecular scale with basis material
It closes, plays apparent reinforcing effect, toughening effect can also be played for hydrogel.In order to which the particle for further increasing aerosol is strong
Degree, enhances natural polysaccharide copper alginate cross-linked structure using inorganic reinforcement and graphene oxide.Enhanced seaweed
Sour copper aerosol catalytic agent has good mechanical strength.
Summary of the invention
1. the object of the present invention is to from the angle of MOLECULE DESIGN, using inorganic reinforcement and graphene oxide to day
Right polysaccharide copper alginate cross-linked structure is enhanced, and obtains high-strength alginic acid copper water colloidal sol, then pass through freeze-drying means, system
The standby porous metals copper alginate aerosol with the inorganic reinforcement of different content.Overcome the machine of copper alginate aerosol catalytic agent
The low disadvantage of tool performance.
The preparation step of silica toughening copper alginate aerosol is as follows:
The first step is dissolved in 50-400 mg graphene oxide in 30 ml distilled water, and sonicated 10 min fills graphene
It is dispersed in water, obtains solution A.
Second step, by 1.0-4.0 g sodium alginate, 2-25 mL ethyl orthosilicate, 1-15mL ethyl alcohol, 10 drop 0.15mol/L
Hydrochloric acid, 5ml glycerine is that 2:1 is added in solution A with ethyl orthosilicate and ethyl alcohol volume ratio, carries out mechanical stirring, until
Mixture sufficiently dissolves, and obtains mixture B.
The whipping temp of mixture B is raised to 80 DEG C by third step, continues to stir 1h, ethyl alcohol is allowed to volatilize away.
4th step, compound concentration is the CuCl of 0.1-0.4 mol/L respectively2Solution, it is spare.
The mixture B dissolved is instilled in ready 96 well culture plate mold, then is dipped in preparation by the 5th step
In good salting liquid, 20 h are reacted in thermostat water bath.
6th step, takes out mold from water-bath, obtains hydrogel, with distilled water flushing, until washing lotion is colourless, then
The hydrogel rinsed is put into 10 h of precooling in -10 DEG C of refrigerator.
7th step is put into pre-freeze good hydrogel in freeze drier and is dried to get finished product, such as Fig. 1.
2. it is provided by the invention using copper alginate aerosol as catalyst, for phenol hydroxylation hydroquinone and neighbour
The method of benzenediol, step and condition are as follows:
(1) reaction medium is placed in magnetic stirring apparatus, can be heated and in three mouthfuls of reactors of energy constant temperature；Reaction medium is
Water, ethyl alcohol or acetonitrile；The reaction medium is preferably water.
(2) mass ratio of phenol and catalyst copper alginate aerosol is 10:1-100:1, mole of phenol and hydrogen peroxide
Than are as follows: the proportion of 2:1-1:3, the volume mL of the quality g and reaction medium of phenol are 1:30；
(3) according to the ratio, by phenol and catalyst copper alginate aerosol be placed in equipped with reaction medium by three mouthfuls of reactors,
Under magnetic agitation, reaction temperature is 30-80 DEG C, and hydrogen peroxide is added drop-wise to three mouthfuls of reactions by constant temperature after temperature reaches set temperature
In device, drop rate is 0.1 mL/min, and beginning calculating reacting time is added dropwise, and the reaction time is 1-6 h, obtains target production
Object；
The utility model has the advantages that (1) it is of the invention silica toughening copper alginate aerosol catalytic agent preparation process it is simple, reactivity
Height, selectivity is good, and good mechanical property, use process is corrosion-free to production equipment, has no adverse effects to environment, is a kind of environment friend
Good type catalyst.(2) catalyst copper alginate Pyrogentisinic Acid's high conversion rate of the invention, up to 77.3%.Suitable for industrialization promotion.
Detailed description of the invention
Fig. 1 is that the silica of the 13rd group of condition preparation and graphene enhance copper alginate aerosol catalytic agent photo.
Specific embodiment:
Combined with specific embodiments below, the present invention is described in detail.
Design multiple groups test:
Experimental condition:
The first step is dissolved in graphene oxide in 30 ml distilled water, and sonicated 10 min is well dispersed in graphene
In water, solution A is obtained.
Second step chooses sodium alginate, and 0.15mol/L hydrochloric acid, glycerine, ethyl orthosilicate and ethanol solution are added to molten
In liquid A, mixture B is obtained, mechanical stirring is carried out, until mixture B sufficiently dissolves.
Third step prepares 0.4 mol/L CuCl2Solution, it is spare.
The mixture B dissolved is instilled in ready 96 well culture plate mold, then is dipped in preparation by the 4th step
0.4 good mol/L CuCl2In solution, 24 h are reacted in 60 DEG C of thermostat water bath.
5th step, takes out mold from water-bath, obtains hydrogel, with distilled water flushing, until washing lotion is colourless, then
The hydrogel rinsed is put into 10 h of precooling in -10 DEG C of refrigerator.
6th step is put into pre-freeze good hydrogel in freeze drier and is dried to get finished product.
Following table is the numerical value of each variable in the multiple groups test of design:
Following table is the compressive strength of the high-strength alginic acid copper aerosol of multiple groups test preparation:
Embodiment 1
13 groups of catalyst for taking multiple groups to test are that 20:1 weighs 1.0 g(10 of phenol by the mass ratio of phenol and catalyst
Mmol), 50 mg of catalyst, the proportion by the volume mL of the quality g and reaction medium of phenol is 1:30, weighs 30 mL water；
The phenol, catalyst and water that weigh up are placed in there-necked flask, there-necked flask is placed in water bath with thermostatic control, under magnetic stirring, works as temperature
It will be weighed 2 mL of hydrogen peroxide (20 mmol) of 1:2 by phenol and hydrogen peroxide molar ratio by dropwise addition speed when degree reaches 70 DEG C
Rate is 0.1 mL/min, is added drop-wise in there-necked flask dropwise, and beginning clock reaction is added dropwise, and the reaction time is 1 h, obtains target
Product.Reaction solution after reacting in embodiment is filtered, separating catalyst and reaction solution.
Catalyst phenol hydroxylation activity data such as table 1.
Table 1
Embodiment 2
The 13rd group of catalyst for taking orthogonal test is that 50:1 weighs 1.0 g(10 of phenol by the mass ratio of phenol and catalyst
Mmol), 20 mg of catalyst is 1:30 g/mL by the quality of phenol and the volume proportion of reaction medium, weighs 30 mL water；?
Phenol, catalyst and the water weighed up is placed in there-necked flask, and there-necked flask is placed in water bath with thermostatic control, under magnetic stirring, works as temperature
It will be that weighed 3 mL of hydrogen peroxide (30 mmol) of 1:3 presses drop rate by phenol and hydrogen peroxide molar ratio when reaching 70 DEG C
It for 0.1 mL/min, is added drop-wise in there-necked flask dropwise, beginning clock reaction is added dropwise, the reaction time is 4 h, obtains target production
Object.Reaction solution after reacting in embodiment is filtered, separating catalyst and reaction solution.
Embodiment 3
The 13rd group of catalyst for taking orthogonal test is that 100:1 weighs 1.0 g(10 of phenol by the mass ratio of phenol and catalyst
Mmol), catalyst 10mg, the proportion by the volume of the quality and reaction medium of phenol is 1:30 g/mL, weighs 30 mL water；
The phenol, catalyst and water that weigh up are placed in there-necked flask, there-necked flask is placed in water bath with thermostatic control, under magnetic stirring, works as temperature
It will be weighed 1 mL of hydrogen peroxide (20 mmol) of 1:1 by phenol and hydrogen peroxide molar ratio by dropwise addition speed when degree reaches 30 DEG C
Rate is 0.1 mL/min, is added drop-wise in there-necked flask dropwise, and beginning clock reaction is added dropwise, and the reaction time is 2 h, obtains target
Product.Reaction solution after reacting in embodiment is filtered, separating catalyst and reaction solution.
Embodiment 4
The 13rd group of catalyst for taking orthogonal test is that 10:1 weighs 1.0 g(10 of phenol by the mass ratio of phenol and catalyst
Mmol), 100 mg of catalyst, the proportion by the volume of the quality and reaction medium of phenol is 1:30 g/mL, weighs 30 mL
Water；The phenol, catalyst and water that weigh up are placed in there-necked flask, there-necked flask is placed in water bath with thermostatic control, under magnetic stirring, when
It will be weighed 0.5 mL of hydrogen peroxide (10 mmol) of 2:1 by drop by phenol and hydrogen peroxide molar ratio when temperature reaches 70 DEG C
Rate of acceleration is 0.1 mL/min, is added drop-wise in there-necked flask dropwise, and beginning clock reaction is added dropwise, and the reaction time is 4 h, is obtained
Target product.Reaction solution after reacting in embodiment is filtered, separating catalyst and reaction solution.
Embodiment 5
The 13rd group of catalyst for taking orthogonal test is that 20:1 weighs 1.0 g(10 of phenol by the mass ratio of phenol and catalyst
Mmol), 50 mg of catalyst, the proportion by the volume of the quality and reaction medium of phenol is 1:30 g/mL, weighs 30 mL second
Nitrile；The phenol, catalyst and acetonitrile that weigh up are placed in there-necked flask, there-necked flask is placed in water bath with thermostatic control, under magnetic stirring,
It will be weighed 2 mL of hydrogen peroxide (5 mmol) of 1:2 by dropwise addition by phenol and hydrogen peroxide molar ratio when temperature reaches 70 DEG C
Rate is 0.1 mL/min, is added drop-wise in there-necked flask dropwise, and beginning clock reaction is added dropwise, and the reaction time is 4 h, obtains mesh
Mark product.Reaction solution after reacting in embodiment is filtered, separating catalyst and reaction solution.
Embodiment 6
The 13rd group of catalyst for taking orthogonal test is that 20:1 weighs 1.0 g(10 of phenol by the mass ratio of phenol and catalyst
Mmol), 50 mg of catalyst, the proportion by the volume of the quality and reaction medium of phenol is 1:30 g/mL, weighs 30 mL second
Alcohol；The phenol, catalyst and ethyl alcohol that weigh up are placed in there-necked flask, there-necked flask is placed in water bath with thermostatic control, under magnetic stirring,
It will be weighed 2 mL of hydrogen peroxide (5 mmol) of 1:2 by dropwise addition by phenol and hydrogen peroxide molar ratio when temperature reaches 70 DEG C
Rate is 0.1 mL/min, is added drop-wise in there-necked flask dropwise, and beginning clock reaction is added dropwise, and the reaction time is 4 h, obtains mesh
Mark product.Reaction solution after reacting in embodiment is filtered, separating catalyst and reaction solution.
It is analyzed with gas chromatograph Agilent GC6890, analysis condition: HP-5 capillary column, fid detector, injection port
Temperature is 280 DEG C, and detector temperature is 300 DEG C.It the results are shown in Table 2.Table 2 shows catalyst copper alginate of the invention to benzene
Phenol high conversion rate, up to 76.5% are suitable for industrialization promotion and use.
Table 2
Claims (6)
1. the preparation method of a kind of silica and graphene oxide enhancing copper alginate aerosol, it is characterised in that specific steps
It is as follows:
(1) graphene oxide is added in distilled water, ultrasound is separately added into sodium alginate, ethyl orthosilicate, second to being uniformly dispersed
Alcohol, certain density hydrochloric acid and glycerine, by mechanical stirring until being uniformly mixed；
(2) solution mixed is continued to stir at 80 DEG C, ethyl alcohol is allowed to volatilize away；
(3) gained mixed solution is instilled in mold, mold is immersed in water-soluble copper salt solution；
(4) copper salt solution is put into thermostat water bath, is reacted at a certain temperature, obtain hydrogel；
(5) by gained hydrogel distilled water flushing until removal outer surface metal ion, puts it into -10 DEG C of refrigerators
10 h of precooling；
(6) the good hydrogel of pre-freeze is put into freeze drier and is dried to get finished product.
2. the system of a kind of silica according to claim 1 and graphene oxide enhancing copper alginate aerosol catalytic agent
Preparation Method, it is characterised in that: graphene oxide is put into distilled water, needs to carry out ultrasonic disperse 5-30 min.
3. the preparation side of a kind of silica according to claim 1 and graphene enhancing copper alginate aerosol catalytic agent
Method, it is characterised in that: the quality of the graphene oxide is 50-400 mg, and the volume of ethyl orthosilicate is 2-25 mL, ethyl alcohol
Volume be 1-15 mL, the proportion of ethyl orthosilicate and ethyl alcohol is 1:2, and the quality of sodium alginate is 1-5 g, the concentration of hydrochloric acid
For 0.4mol/L, 5ml glycerine, the concentration of metal salt solution is 0.05-0.50 mol/L.
4. the system of a kind of silica according to claim 1 and graphene oxide enhancing copper alginate aerosol catalytic agent
Preparation Method, it is characterised in that: the mixed solution needs continue to stir 1 h under the conditions of 80 DEG C, and ethyl alcohol is allowed sufficiently to volatilize away.
5. the system of a kind of silica according to claim 1 and graphene oxide enhancing copper alginate aerosol catalytic agent
Preparation Method, it is characterised in that: the temperature that the mixed solution carries out heating water bath is 40-80 DEG C, and the time is 10-25 h.
6. the system of a kind of silica according to claim 1 and graphene oxide enhancing copper alginate aerosol catalytic agent
Preparation Method, it is characterised in that: the enhanced copper alginate aerosol of graphene oxide has good mechanical strength.
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| CN114479816A (en) * | 2022-04-02 | 2022-05-13 | 四川锦盛油田技术服务有限公司 | Foam drainage agent and preparation method thereof |
| CN117229678A (en) * | 2023-11-15 | 2023-12-15 | 四川赛尔科美新材料科技有限公司 | Inorganic silicon sound insulation and heat preservation gel and manufacturing method thereof |
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