CN102614917B - Preparation method of composite carbon base solid acid catalyst - Google Patents
Preparation method of composite carbon base solid acid catalyst Download PDFInfo
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- CN102614917B CN102614917B CN 201210052474 CN201210052474A CN102614917B CN 102614917 B CN102614917 B CN 102614917B CN 201210052474 CN201210052474 CN 201210052474 CN 201210052474 A CN201210052474 A CN 201210052474A CN 102614917 B CN102614917 B CN 102614917B
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Abstract
The invention relates to preparation of a catalyst, in particular to a preparation method of a composite carbon base solid acid catalyst. The preparation method comprises the following processing steps of: preparing composite resin; carbonizing; washing with water; performing suction filtration; drying; and performing sulfonation reaction. The technical scheme provided by the invention has the characteristics that: 1, the raw materials have wide sources and are readily available; according to the preparation method, a renewable biomass base is used as a raw material, i.e., carbohydrate is used as the raw material, so that the raw materials are low in cost and have wide sources; 2, after the biomass base is modified by using a cross-linking agent, carbonized resin is formed after carbonization, so that a multi-condensed-ring carbon nuclear structure matrix is more favorably formed than direct carbonation of biomass, and meanwhile, the mechanical strength and the stability of the carbonized resin are higher than those in the prior art; and 3, the carbonized resin has low probability of forming easily soluble small molecular compound in a sulfonation process, so that more sulfonic acid groups can be linked; and thus, the reusability, the catalytic activity and the acidity of the composite carbon base solid acid catalyst are greatly improved.
Description
Affiliated technical field
The present invention relates to a kind of preparation of catalyst, particularly the preparation method of composite carbon based solid acid catalyst.
Background technology
Solid acid catalyst is the inevitable choice that reaches green chemical industry, and the solid acid catalyst that at present research is both at home and abroad reported mainly contains Sulfonic Acid Resin, polytetrafluoroethylene (PTFE) sulfonate resin and solid carbon sulfonic acid catalyst.There is the shortcoming of poor heat resistance in Sulfonic Acid Resin, has so just limited its range of application; Although the polytetrafluoroethylene (PTFE) sulfonate resin has higher heat endurance, its expensive price is restricted its application in chemical process.
In recent years, the preparation of solid carbon sulfonic acid catalyst and application have been subject to the attention of academia.People have developed take multiring aromatic hydrocarbon, carbohydrate (such as glucose etc.), natural materials (such as timber, walnut, millet and lignin etc.) as raw material, through partially carbonized, then sulfuric acid sulfonation and many kinds of solids charcoal sulfonic acid, and in some Minute Organic Synthesis and biomass conversion, have good catalytic effect.But the material that these methods obtain is subjected to the restriction in carbon source matrix source, or raw material sources are expensive, or the product powderization seriously causes bad mechanical strength etc.; Prepared material belongs to pulverous flexible material, and the surface is compact texture, and the aperture is undeveloped and be difficult to regulation and control, and acidity is not that very desirable and surperficial acidic site runs off in liquid phase reactor easily.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art, provide that a kind of catalytic activity is higher, stability and reusability is good, the preparation method of low production cost, composite carbon based solid acid catalyst that acidity is higher.
For achieving the above object, technical scheme of the present invention is: a kind of preparation method of composite carbon based solid acid catalyst, and its processing step is:
1) preparation composite resin: by weight 1: 5-10 is that 10% the sodium humate aqueous solution mixes under stirring with carbohydrate and weight percent concentration, then by the 5-10% of the powder gross weight of the above-mentioned sodium humate aqueous solution and carbohydrate and crosslinking agent and the catalyst of 5-10.5%, at N
2Under the atmosphere, stir, be heated to 80-98 ℃, react after 4-12 hour, dehydration, drying get compound resin under vacuum state;
2) carbonization: above-mentioned compound resin is ground to about 200 orders, at 300-450 ℃, N
2After carrying out carbonization 4-12 hour under the atmosphere, be cooled to room temperature;
3) in the carbide resin powder that washing suction filtration and oven dry: in above-mentioned steps 2) obtains, the hot water that adds 80-100 ℃ washs, and suction filtration is until filtrate after neutrality, at the 100-120 ℃ of lower 6-12h of drying, gets the carbide resin powder;
4) sulfonating reaction: the carbide resin powder of getting 1 weight portion mixes mutually with the 10-26ml sulfonating agent, at N
2Atmosphere with stir down, behind 80-240 ℃ of reaction 6-16h, be cooled to room temperature, put into cold water and carry out suction filtration and reclaim sulfonating agent, then with 80-100 ℃ hot water wash, suction filtration is until filtrate is clarified, and do not have SO
4 2-Till being detected, at 110-120 ℃ of lower oven dry 2-6h, get the composite carbon based solid acid catalyst.
Above-mentioned carbohydrate is the mixture of a kind of or its arbitrary proportion in sucrose, glucose, starch, cellulose, the lignin.
Above-mentioned crosslinking agent is the mixture of a kind of or its arbitrary proportion in formaldehyde, benzaldehyde and the derivative thereof in the aldehyde compound.
Above-mentioned catalyst is the salt of strong acid or transition metal.
The vacuum of above-mentioned vacuum state is about 0.08MPa.
The above-mentioned sulfonating agent concentration that is weight percentage is 98% concentrated sulfuric acid or chlorosulfonic acid or oleum.。
The characteristics of technical solution of the present invention: 1, raw material sources extensively, be easy to get.Utilization of the present invention can be again biomass-based be raw material, namely carbohydrate of the present invention is raw material, has cheap, the wide material sources of cost of material; 2, adopt crosslinking agent to advance the carbide resin that forms after the carbonization with biomass-based through after the modification, more be conducive to form than the direct carbonization living beings and many carbon nuclear structure matrix of condensed ring, the mechanical strength of this carbide resin and stability are higher than prior art simultaneously; 3, carbide resin of the present invention is difficult for forming diffluent micromolecular compound in sulfonation process, thereby can link more sulfonic acid group, and reusability, catalytic activity and the acidity of this composite carbon based solid acid catalyst are greatly improved.
The specific embodiment
Below will the present invention is further elaborated by specific embodiment:
Embodiment 1:
(1) preparation composite resin:
At room temperature, get the sucrose 4g of granularity about 190 μ m, join and fill in the beaker that the 40g mass concentration is 10% sodium humate solution, after magnetic agitation stirs about 30 minutes and all uses, transfer them to and be furnished with electromagnetic agitation, in the there-necked flask of thermometer, reflux condensing tube and water knockout drum, then add 2.3ml as the formalin of crosslinking agent and the 2.2g p-methyl benzenesulfonic acid as catalyst; Pass into N
2Stir, add hot reflux, when heating-up temperature reaches 80 ℃, keep temperature-resistant reaction 12h; Then dry 4h after the vacuum dehydration under 0.08MPa gets the block composite resin of black;
(2) carbonization
After being ground to above-mentioned block composite resin about 200 orders, place retort at N
2Protection is lower, behind 450 ℃ of carbonization 8h, and cool to room temperature;
(3) washing suction filtration and oven dry:
With the composite resin powder after the above-mentioned carbonization, the hot water that adds about 80 ℃ washs, and suction filtration gets bright black carbide resin powder until the filtrate clarification for after the neutrality, places baking oven dried, collects for subsequent use;
(4) sulfonating reaction:
In the there-necked flask that has electromagnetic agitation, thermometer, reflux condensing tube, add the above-mentioned carbide resin powder for subsequent use of 2g and the 20ml98% concentrated sulfuric acid, oil bath adds thermal agitation, passes into N
2, behind 120 ℃ of reaction 10h, will be cooled to room temperature and suction filtration and reclaim the concentrated sulfuric acid, then with about 80 ℃ hot water solid is washed, with the distilled water washing, suction filtration does not have SO until filtrate is clarified again
4 2-Till being detected, dry to get target product; Titration records the acid amount and is 1.23mmol/g.
Embodiment 2-7:
On the basis of the processing step of above-described embodiment 1, change carbohydrate, crosslinking agent, catalyst and technology condition, specifically see the following form:
In the above-described embodiments, gained sulfonation solid acid acidity (mmol/g) is between 1.52-1.86.
Embodiment 8-12:
On the processing step basis of above-mentioned arbitrary embodiment, change the described process conditions of following table in the sulfonating reaction step, the results are shown in following table:
In the above-described embodiments, drying time and temperature its objective is drying materials is got final product according to concrete condition oven dry 2-6h under 110-120 ℃ of material.
Above-described embodiment gained composite carbon based solid acid catalyst is respectively applied in catalytic esterification and the catalyzing and condensing reaction, and its process is seen following embodiment.
Embodiment 13:
Catalytic esterification 1: having the thermostatical oil bath, magnetic stirring apparatus, thermometer, water knockout drum, add the 0.2mol propionic acid in the 150ml there-necked flask of condenser pipe, 0.24mol normal propyl alcohol, catalyst 1.25g with aqua cyclohexane 5ml and embodiment 1 preparation, behind the heating return stirring 1.5h, stop reaction, question response solution is cooled to room temperature, emit the water layer in the water knockout drum, merge organic phase, filter to isolate catalyst, use first twice of equal-volume saturated sodium-chloride water washing, again with isopyknic distilled water washing once, after a period of time, 120～124 ℃ of cuts are collected in air-distillation through anhydrous magnesium sulfate drying, and yield is 70.53%.Catalyst of the present invention is reused 3 times, and catalytic activity is substantially constant.
Catalytic esterification 2: the catalyst 0.3g that in the 50mL round-bottomed flask, adds 0.075mol phenmethylol, 0.09mol n Propanoic acid, 6ml cyclohexane and embodiment 3 preparations, place microwave instrument chamber, load onto water knockout drum and reflux condensing tube, set 100 ℃ of microwave temperature, time 10min, power 400w, reflux water-dividing under microwave.After reaction finished, the question response liquid cooling was but emitted the water layer in the water knockout drum, merged organic phase, with saturated common salt water washing 2～3 times, used anhydrous CaCl again
2Distill after the drying, collect 216～220 ℃ of cuts, yield is 91.03%.
Embodiment 14
Except for the following differences, all the other are identical with catalytic esterification 2 among the embodiment 11, after reaction finishes, filtering recovering catalyst, need not any processing, continue reaction, catalyst is reused relation such as the following table between inferior and the yield. show that by experiment the composite carbon based solid acid catalyst that above-described embodiment is produced is used for catalytic esterification.
Catalyst Reusability number of times is investigated
Embodiment 15
Catalyzing and condensing reaction: with the catalyst of 0.4g embodiment 4 preparations, 0.075mol benzaldehyde, 0.1125mol ethylene glycol and 6ml cyclohexane add in the 50mL round-bottomed flask successively, fully vibration, put into micro-wave oven and add the reflux water-dividing device, 100 ℃ of set temperatures, time 30min, power 300W, start microwave radiometer, finish Deng reaction, after temperature drops to room temperature, emit the water layer in the water knockout drum, merge organic phase, use the saturated aqueous common salt washed twice, again with distillation washing once, afterwards use anhydrous magnesium sulfate drying half an hour, air-distillation, collect 210～218 ℃ of cuts, yield is 90.00%.Catalyst of the present invention is reused 5 times, and catalytic activity is substantially constant.
Embodiment 16
Catalysis one kettle way, three component mannich reaction: the catalyst 0.28g that in the 50mL single necked round bottom flask, adds successively 3mL absolute ethyl alcohol, 12mmol cyclohexanone, 10mmol p-tolyl aldehyde, 10mmol parachloroanilinum and embodiment 1 preparation, stirring reaction 1h under the room temperature has a large amount of solids to separate out.After the ethanol thermosol filtered out catalyst, reduced pressure concentration got product with ethyl alcohol recrystallization, and productive rate is that 73.44%, anti/syn is 97: 3.
Show that by experiment the composite carbon based solid acid catalyst that above-described embodiment is produced is used for the catalyzing and condensing reaction, catalyst is reused 5 times, and catalytic activity is substantially constant.
Claims (6)
1. the preparation method of a composite carbon based solid acid catalyst, its processing step is:
1) preparation composite resin: 1:5-10 is that 10% the sodium humate aqueous solution mixes under stirring with carbohydrate and mass concentration by weight, then by 5-10% and 5-10.5% crosslinking agent and catalyst of the above-mentioned sodium humate aqueous solution and carbohydrate gross weight, at N
2Under the atmosphere, stir, be heated to 80-98 ℃, react after 4-12 hours, dehydration, drying get compound resin under vacuum state;
2) carbonization: above-mentioned compound resin is ground to 200 orders, at 300-450 ℃, N
2Carry out carbonization under the atmosphere after 4-12 hours, be cooled to room temperature;
3) in the carbide resin powder that washing suction filtration and oven dry: in above-mentioned steps 2) obtains, the hot water that adds 80-100 ℃ washs, and suction filtration is until filtrate after neutrality, dries to get the carbide resin powder;
4) sulfonating reaction: get the carbide resin powder of 1 weight portion and the sulfonating agent of 12-46 weight portions and mix mutually, at N
2Under atmosphere and the stirring, be heated to 80-240 ℃ of reaction 6-16h after, be cooled to room temperature, put into cold water and carry out suction filtration and reclaim sulfonating agent, then with 80-100 ℃ hot water wash, suction filtration is until filtrate is clarified, and do not have SO
4 2-Till being detected, dry to get the composite carbon based solid acid catalyst.
2. the preparation method of composite carbon based solid acid catalyst according to claim 1 is characterized in that above-mentioned carbohydrate is the mixture of a kind of or its arbitrary proportion in sucrose, glucose, starch, cellulose, the lignin.
3. the preparation method of described composite carbon based solid acid catalyst according to claim 2 is characterized in that above-mentioned crosslinking agent is the mixture of a kind of or its arbitrary proportion of formalin, benzaldehyde in the aldehyde compound.
4. the preparation method of composite carbon based solid acid catalyst according to claim 3 is characterized in that above-mentioned catalyst is strong acid or zinc chloride.
5. the preparation method of composite carbon based solid acid catalyst according to claim 4, the vacuum that it is characterized in that above-mentioned vacuum state is 0.08MPa.
6. the preparation method of composite carbon based solid acid catalyst according to claim 5 is characterized in that above-mentioned sulfonating agent is 98% concentrated sulfuric acid or chlorosulfonic acid or oleum.
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| CN104529707B (en) * | 2015-01-05 | 2016-05-04 | 广西民族大学 | Utilize the method for the synthetic terpinol of carbon-based solid acid catalyzing turpentine oil one step hydration |
| CN106268940A (en) * | 2016-08-10 | 2017-01-04 | 华南理工大学 | Xylan base carbon-based solid acid and the method being catalyzed and synthesized benzodiphenylene oxide compounds by it |
| CN107890882B (en) * | 2017-11-07 | 2020-06-23 | 济南大学 | Method for preparing high-acid-density solid catalyst by impregnation-polymerization method |
| CN111036298A (en) * | 2019-12-17 | 2020-04-21 | 华侨大学 | Preparation method and application of natural walnut shell powder sulfonic acid catalyst |
| CN112717953B (en) * | 2020-12-23 | 2022-01-18 | 浙江大学 | Carbon-based solid acid catalyst, preparation method and method for applying carbon-based solid acid catalyst to biomass hydrothermal conversion |
| 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 |
| CN114797898A (en) * | 2022-04-29 | 2022-07-29 | 合肥工业大学 | Solid carbon sulfonic acid catalyst, preparation method and application thereof |
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| CN102078823A (en) * | 2010-11-25 | 2011-06-01 | 北京大学 | Carbon-based solid acid catalyst and preparation method thereof |
| CN102218342A (en) * | 2011-04-02 | 2011-10-19 | 华东理工大学 | Preparation method of high efficient sulfonated carbon solid acid catalyst |
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| CN102078823A (en) * | 2010-11-25 | 2011-06-01 | 北京大学 | Carbon-based solid acid catalyst and preparation method thereof |
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