CN103084187B - Carbon-based solid acid and preparation method thereof - Google Patents

Carbon-based solid acid and preparation method thereof Download PDF

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CN103084187B
CN103084187B CN201210547711.1A CN201210547711A CN103084187B CN 103084187 B CN103084187 B CN 103084187B CN 201210547711 A CN201210547711 A CN 201210547711A CN 103084187 B CN103084187 B CN 103084187B
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carbon
shell
solid acid
acid
solid
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CN103084187A (en
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任庆功
陈诚
李为民
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Suzhou science and Technology City Biomedical Technology Development Co., Ltd
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Changzhou University
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Abstract

The invention provides a carbon-based solid acid and a preparation method thereof. The preparation method of carbon-based solid acid comprise the steps of: taking fresh fruit shells as raw materials, washing, drying and crushing the fresh fruit shells into needed particle size, adding into an activating agent solution for soaking and activating, drying the activated fruit shells, carbonizing under the heating condition to prepare activated carbon, grinding the prepared activated carbon materials into powder, boiling in an acid solution, then leaching, bleaching with distilled water and drying, heating the dried activated carbon materials, sulfonating through a sulfonating agent, slowly pouring the sulfonated mixture solution into cold water and continuously stirring, leaching and drying to obtain black solid powder, namely carbon-based solid acid. The carbon-based solid acid prepared has the advantages of being large in specific surface area and higher in catalytic property.

Description

A kind of carbon-based solid acid and preparation method thereof
Technical field
The present invention relates to a kind of solid acid and preparation method thereof, particularly a kind of carbon-based solid acid and preparation method thereof.
Background technology
Due to the extensive use of acid catalyst and the requirement of green chemical industry, in recent years with the exploitation of the low-carbon (LC) production green catalysis technique that is target and catalyst, become the focus of catalyticing research.Only take the improvement of technique and catalyst could realize scientific and technical innovation to combine with environmental protection, just can bring the simultaneous growth of the high benefit of enterprise and social high benefit.For overcoming the corrosivity of liquid acid catalyst to production equipment; Normal and raw material and product form homogeneous phase body, cause the numerous and diverse of post-reaction treatment; Technique is unfavorable for realize the shortcomings such as continuous prodution requirement, solid acid progressively replaces traditional liquid acid catalyst, and the every field making it to be widely used in Chemical Manufacture is inevitable developing direction.By the exploitation of people to solid acid nearly half a century, up to the present, the chemical enginnering process participated in by liquid acid before existing a large amount of replace by solid acid.
In recent years, the Sulfonated solid acid of carbon back as a kind of newly, can the solid acid of strong Bronsted acidity and stability be kept and receive much attention in water.According to the summary to document, the synthesis for the Sulfonated solid acid of carbon back roughly has two kinds of thinkings: the first is that the poly-ring aromatic compounds of p-sulfonic acid carries out incomplete carbonization.In this synthetic method, be the first stage reacted to the sulfonated of aromatic, the Sulfonated aromatic then obtained heats and carries out incomplete carbonization under the effect of the concentrated sulfuric acid.But in the liquid phase reactor of temperature more than 100 DEG C, easily there is the solution-off of aromatization platform thing or cause serious inactivation in the solid acid prepared of this method.In addition, the experimental implementation of carrying out carbonization under the condition of high-temperature concentrated sulfuric acid is very dangerous, therefore also limits the popularization of this test method; The synthetic method of the second is sulfonated again after first carrying out incomplete carbonization to organic compound.The proposition of this synthetic method is on the basis of synthesizing based on safety, with low toxicity or nontoxic material for target material prepared by raw material.Sucrose common in daily life, glucose, starch, cellulose etc. are all used as carbon source at high temperature isolated air roasting, make it to resolve into the amorphous carbon containing many little carbon plates.On amorphous carbon, sulfonic acid group is introduced again by Sulfonated method.Relative to the first one-tenth method, the method is not only simple but also security is good.In addition, the advantage place that the highly active solid acid with practical value is also this synthetic method can be synthesized from the resource that occurring in nature exists in a large number.
Takagaki etc. are that carbon-based solid acid (Acid-catalyzed reactions on flexiblepolycyclic aromatic carbon in amorphous carbon prepared by raw material with glucose, Takagaki et al, Catal Today, 2006); It is that novel carbon-based solid acid catalyst (carbon-based solid acid catalysis high acid value biodiesel raw material deacidification effect, king superintends and directs, EI, 2009,25) prepared by raw material with starch that king superintends and directs etc.; The people such as Ma Fang are that carbon-based solid acid catalyst (technical study of maize straw solid acid catalyst and catalytically synthesizing biological diesel oil, Ma Fang etc., Journal of Northwest Sci Tech University of Agriculture and Forestry, 2010,38) prepared by raw material with maize straw; Li Liqiang take active carbon from coal as carrier, and sodium humate is that carbon source has prepared composite carbon based solid acid (Synthesis and applications of composite carbon base solid acid catalyst, Li Liqiang, Ningxia University's master thesis, 2010).
In prior art, the synthesis initiation material of carbon-based solid acid is greatly mainly with sucrose, glucose, starch, cellulose, and cost is higher and cause the wasting of resources.In the prior art preparing carbon-based solid acid, the product finally obtained is mostly atresia, and specific area is low, bad mechanical property, which limits a lot of reactant molecules particularly those macromolecular reaction things close to the active sites of catalyst surface.
Summary of the invention
Technical problem to be solved by this invention is: in prior art, and the cost of material that the preparation of carbon-based solid acid adopts is higher and cause the wasting of resources; The product specific area prepared is lower.
In order to solve this technical problem, the technical solution used in the present invention is: the invention provides a kind of carbon-based solid acid, and this carbon-based solid acid utilizes fresh shell for raw material, is prepared from, and obtained carbon-based solid acid specific area is at 1000m 2/ more than g, acid number is at more than 2.5mmol/L.
Present invention also offers a kind of method preparing above-mentioned carbon-based solid acid, concrete steps are:
(1) pretreatment of fresh shell: air-dry fresh shell water is washed till repeatedly and does not have impurity, then the shell of wash clean is put into baking oven dry, remove moisture, the shell that screening product is compared, 10 ~ 50 orders are crushed to for subsequent use in disintegrating machine, as preferably: fresh shell is the shell of nut, is selected from a kind in chestnut shell, pine nut shell, walnut shell, cocoanut shell, Shell of Water Chestnut or peanut shell or several compositions
As preferably: the granularity after fragmentation is 10 ~ 30 orders, further: granularity is 20 orders;
(2) activation of shell: by solid-liquid ratio 1:2 ~ 20g/mL, pretreated shell being joined activator concentration is soak 2 ~ 12h in the solution of 20 ~ 50wt%, is then dried in an oven by soaked shell, to remove unnecessary moisture,
As preferably: solid-liquid ratio is 1:2 ~ 10g/mL, further: solid-liquid ratio is 1:5g/mL,
As preferably: activator is slaine or inorganic acid, be selected from a kind in zinc chloride, aluminium chloride, ammonium chloride, calcium chloride, hydrogen chloride, phosphoric acid, sulfuric acid, nitric acid, potassium sulfide or molysite or several compositions, further: activator solution is the zinc chloride of 30wt%;
(3) carbonization of shell: by activating the shell obtained in step (2), be heated to 400 ~ 600 DEG C under protective atmosphere, carbonization 2 ~ 15h; prepare active carbon, by active carbon grind into powder, boil in acid solution; then suction filtration, obtains absorbent charcoal material with after distilled water rinsing, drying
As preferably: protective atmosphere is selected from a kind or several combination atmosphere in nitrogen, carbon dioxide, argon gas, helium or neon, further: protective atmosphere is nitrogen and/or carbon dioxide,
As preferably: heating-up temperature is 400 ~ 500 DEG C, further: temperature is 450 DEG C,
As preferably: carbonization time is 2 ~ 10h, further: carbonization time is 2 ~ 6h,
As preferably: acid solution is selected from a kind or several in hydrochloric acid, phosphoric acid, citric acid, sulfuric acid or oxalic acid, and its concentration is 0.5 ~ 1.5mol/L, further: acid solution is the hydrochloric acid of 1mol/L;
(4) sulfonation of absorbent charcoal material: by the absorbent charcoal material obtained in step (3), under 80 ~ 200 DEG C of conditions, through sulfonating agent sulfonation 6 ~ 15h, the mixed liquor after sulfonation is gently poured in cold water and is also constantly stirred, suction filtration, oven dry gained black solid powder are carbon-based solid acid
As preferably: sulfonation temperature is 120 ~ 200 DEG C, further: sulfonation temperature is 150 DEG C,
As preferably: sulfonation time is 6 ~ 10h, further: sulfonation time is 8 ~ 10h,
As preferably: sulfonating agent is selected from a kind or several combinations in the concentrated sulfuric acid, oleum, chlorosulfonic acid or sulfamic acid, further: sulfonating agent is selected from the concentrated sulfuric acid, oleum and chlorosulfonic acid a kind or several combinations, more further: sulfonating agent is the concentrated sulfuric acid.
The present invention has following beneficial effect:
Select fresh shell as raw material, prepare carbon-based solid acid, reduce the preparation cost of solid acid, open the new way of shell high-qualityization, effectively improve the utilization rate to shell, meet national current sustainable development policy.Compare in prior art, take fused ring compound as the reaction condition safety that carbon-based solid acid prepared by raw material, product color is good, and obtained carbon-based solid acid has larger specific area, has good catalytic effect.
Accompanying drawing explanation
Fig. 1 is the process chart being prepared the method for carbon-based solid acid by fresh shell of the present invention.
Detailed description of the invention
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment is only help to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1:
The pretreatment of fresh shell:
Get fresh District, Xinyang Area, Henan Province chestnut shell (yellowish-brown), repeatedly wash away dust and the impurity on chestnut shell surface with water, until the water washed out is as clear as crystal, then chestnut shell is put into the baking oven of 120 DEG C, dry 2h, remove the moisture in chestnut shell.In the chestnut shell of drying, screen product good chestnut shell mutually, in disintegrating machine, be crushed to 10-30 order, take 200g, count shell 1.
Embodiment 2:
The pretreatment of fresh shell:
Get fresh Tonghua, Jilin Province pine nut shell (brown), repeatedly wash away dust and the impurity on pine nut shell surface with water, until the water washed out is as clear as crystal, then pine nut shell is put into the baking oven of 120 DEG C, dry 2h, remove the moisture in pine nut shell.In the pine nut shell of drying, screen product good pine nut shell mutually, in disintegrating machine, be crushed to 10-30 order, take 200g, count shell 2.
Embodiment 3:
The pretreatment of fresh shell:
Get fresh Kuqa walnut shell (yellowish-brown), repeatedly wash away dust and the impurity on walnut shell surface with water, until the water washed out is as clear as crystal, then walnut shell is put into the baking oven of 120 DEG C, dry 2h, remove the moisture in walnut shell.In the walnut shell of drying, screen product good walnut shell mutually, in disintegrating machine, be crushed to 10-30 order, take 200g, count shell 3.
Embodiment 4:
The pretreatment of fresh shell:
Get fresh Shandong, Shandong flower peanut shell (yellowish-brown), repeatedly wash away dust and the impurity on peanut shell surface with water, until the water washed out is as clear as crystal, then peanut shell is put into the baking oven of 120 DEG C, dry 2h, remove the moisture in peanut shell.In the peanut shell of drying, screen product good peanut shell mutually, in disintegrating machine, be crushed to 10-30 order, take 200g, count shell 4.
Embodiment 5:
Choosing through pretreated fresh shell is that raw material carries out activator solution immersion, and then under protective atmosphere, carbonization-activation prepares active carbon material.
In 400mL beaker, add 43g activator, in beaker, pour 100mL distilled water into, stirring and dissolving, in activator solution, add pretreated fresh shell 30g, stir 5min, under normal temperature, flood 8h.Then the sample flooded is put into 110 DEG C of baking ovens and dry 2h, remove moisture.Sample after drying is placed in dry pot, puts into electric tube furnace, under the protective atmosphere of nitrogen, at 450 DEG C, be prepared into activated carbon through carbonization-activation 3h.After electric tube furnace cooling, take out active carbon wherein, grinding, boil 30min with the hydrochloric acid of 1mol/L, being then washed till PH with distilled water is about 7, dries and obtains absorbent charcoal material.
Choose shell 1 for raw material, flood as activator with liquor zinci chloridi, obtained active carbon 1;
Choose shell 1 for raw material, flood as activator with phosphoric acid solution, obtained active carbon 2;
Choose shell 2 for raw material, flood as activator with liquor zinci chloridi, obtained active carbon 3;
Choose shell 2 for raw material, flood as activator with phosphoric acid solution, obtained active carbon 4;
Choose shell 3 for raw material, flood as activator with liquor zinci chloridi, obtained active carbon 5;
Choose shell 3 for raw material, flood as activator with phosphoric acid solution, obtained active carbon 6;
Choose shell 4 for raw material, flood as activator with liquor zinci chloridi, obtained active carbon 7;
Embodiment 6:
Choose active carbon 1 for raw material and prepare carbon-based solid acid:
In the four-hole boiling flask of 250mL, add activated carbon 10g, pour the concentrated sulfuric acid (98% concentrated sulfuric acid) 100mL into, four-hole boiling flask is put into oil bath pan, at place's interface access nitrogen of four-hole boiling flask, another interface is as the outlet of nitrogen, and nitrogen outlet accesses in water.Oil bath is warming up to 120 DEG C, sulfonation 8h.After reaction terminates, mixed liquor is slowly poured in cold water, and constantly stirs, suction filtration solution after cooling, with distilled water washing black solid to neutral, vacuum drying 5h, finally obtained carbon-based solid acid.The means of employing X-ray diffraction (XRD), infrared spectrum (FT-IR) characterize product, and result shows, carbon-based solid acid is by being connected with sulfonic group (-SO 3the amorphous carbon of fragrant carbon plate composition H); Recording specific area by nitrogen adsorption BET method is 1269m 2/ g, recording sour density by NaOH solution titration is 2.83mmol/L.
Embodiment 7:
Choose activated carbon 2 for raw material and prepare carbon-based solid acid:
In the four-hole boiling flask of 250mL, add activated carbon 10g, pour oleum 135mL into, four-hole boiling flask is put into oil bath pan, at place's interface access nitrogen of four-hole boiling flask, another interface is as the outlet of nitrogen, and nitrogen outlet accesses in water.Oil bath is warming up to 130 DEG C, sulfonation 8h.Processing method, with embodiment 6, finally obtains carbon-based solid acid.The means of employing X-ray diffraction (XRD), infrared spectrum (FT-IR) characterize product, and result shows, carbon-based solid acid is by being connected with sulfonic group (-SO 3the amorphous carbon of fragrant carbon plate composition H); Recording specific area by nitrogen adsorption BET method is 1127m 2/ g, recording sour density by NaOH solution titration is 2.48mmol/L.
Embodiment 8:
Choose activated carbon 3 for raw material and prepare carbon-based solid acid:
In the four-hole boiling flask of 250mL, add activated carbon 10g, pour the concentrated sulfuric acid (98% concentrated sulfuric acid) 150mL into, four-hole boiling flask is put into oil bath pan, at place's interface access nitrogen of four-hole boiling flask, another interface is as the outlet of nitrogen, and nitrogen outlet accesses in water.Oil bath is warming up to 150 DEG C, sulfonation 9h.Processing method, with embodiment 6, finally obtains carbon-based solid acid.The means of employing X-ray diffraction (XRD), infrared spectrum (FT-IR) characterize product, and result shows, carbon-based solid acid is by being connected with sulfonic group (-SO 3the amorphous carbon of fragrant carbon plate composition H); Recording specific area by nitrogen adsorption BET method is 1326m 2/ g, recording sour density by NaOH solution titration is 3.52mmol/L.
Embodiment 9:
Choose activated carbon 4 for raw material and prepare carbon-based solid acid:
In the four-hole boiling flask of 250mL, add activated carbon 10g, pour oleum 80mL into, four-hole boiling flask is put into oil bath pan, at place's interface access nitrogen of four-hole boiling flask, another interface is as the outlet of nitrogen, and nitrogen outlet accesses in water.Oil bath is warming up to 150 DEG C, sulfonation 9h.Processing method, with embodiment 6, finally obtains carbon-based solid acid.The means of employing X-ray diffraction (XRD), infrared spectrum (FT-IR) characterize product, and result shows, carbon-based solid acid is by being connected with sulfonic group (-SO 3the amorphous carbon of fragrant carbon plate composition H); Recording specific area by nitrogen adsorption BET method is 1274m 2/ g, recording sour density by NaOH solution titration is 1.93mmol/L.
Embodiment 10:
Choose activated carbon 5 for raw material and prepare carbon-based solid acid:
In the four-hole boiling flask of 250mL, add activated carbon 10g, pour the concentrated sulfuric acid (98% concentrated sulfuric acid) 110mL into, four-hole boiling flask is put into oil bath pan, at place's interface access nitrogen of four-hole boiling flask, another interface is as the outlet of nitrogen, and nitrogen outlet accesses in water.Oil bath is warming up to 160 DEG C, sulfonation 10h.Processing method, with embodiment 6, finally obtains carbon-based solid acid.The means of employing X-ray diffraction (XRD), infrared spectrum (FT-IR) characterize product, and result shows, carbon-based solid acid is by being connected with sulfonic group (-SO 3the amorphous carbon of fragrant carbon plate composition H); Recording specific area by nitrogen adsorption BET method is 982m 2/ g, recording sour density by NaOH solution titration is 1.63mmol/L.
Embodiment 11:
Choose activated carbon 6 for raw material and prepare carbon-based solid acid:
In the four-hole boiling flask of 250mL, add activated carbon 10g, pour oleum 95mL into, four-hole boiling flask is put into oil bath pan, at place's interface access nitrogen of four-hole boiling flask, another interface is as the outlet of nitrogen, and nitrogen outlet accesses in water.Oil bath is warming up to 180 DEG C, sulfonation 8h.Processing method, with embodiment 6, finally obtains carbon-based solid acid.The means of employing X-ray diffraction (XRD), infrared spectrum (FT-IR) characterize product, and result shows, carbon-based solid acid is by being connected with sulfonic group (-SO 3the amorphous carbon of fragrant carbon plate composition H); Recording specific area by nitrogen adsorption BET method is 1073m 2/ g, recording sour density by NaOH solution titration is 2.47mmol/L.
Embodiment 12:
Choose activated carbon 7 for raw material and prepare carbon-based solid acid:
In the four-hole boiling flask of 250mL, add activated carbon 10g, pour the concentrated sulfuric acid (98% concentrated sulfuric acid) 120mL into, four-hole boiling flask is put into oil bath pan, at place's interface access nitrogen of four-hole boiling flask, another interface is as the outlet of nitrogen, and nitrogen outlet accesses in water.Oil bath is warming up to 200 DEG C, sulfonation 9h.Processing method, with embodiment 6, finally obtains carbon-based solid acid.The means of employing X-ray diffraction (XRD), infrared spectrum (FT-IR) characterize product, and result shows, carbon-based solid acid is by being connected with sulfonic group (-SO 3the amorphous carbon of fragrant carbon plate composition H); Recording specific area by nitrogen adsorption BET method is 856m 2/ g, recording sour density by NaOH solution titration is 1.68mmol/L.
Embodiment 13:
Carbon-based solid acid in example 6 is used for catalysis for preparing biodiesel oil, soybean oil and methyl alcohol (mol ratio 1:3) is added in the there-necked flask of 250mL, carbon-based solid acid addition is 8% of soybean oil and methyl alcohol gross mass, and at 65 DEG C, react 2h, biodiesel conversion rate reaches 93.6%.
Embodiment 14:
Carbon-based solid acid in embodiment 7 is used for catalysis and prepares ethyl acetate, acetic acid and ethanol (mol ratio 1:1) is added in the there-necked flask of 250mL, carbon-based solid acid addition is 8% of acetic acid and total ethanol quality, at 65 DEG C, react 2h, and ethyl acetate productive rate reaches 89.3%.
Embodiment 15:
Carbon-based solid acid in embodiment 8 is used for catalysis and prepares australene isomerization reaction, catalyst: australene=1:20(wt), at 165 DEG C, react 4h, australene conversion ratio reaches 94.87%.
Embodiment 16:
Carbon-based solid acid in embodiment 12 is used for catalysis and prepares epoxy aliphatic ester, fatty acid methyl ester is added in the there-necked flask of 250mL, constant speed drips the hydrogen peroxide accounting for fatty acid methyl ester quality 30%, carbon-based solid acid addition is 8% of fatty acid methyl ester quality, at 80 DEG C, react 6h, epoxide number reaches 4.4%.
The method preparing carbon-based solid acid by fresh shell of the present invention provides the twice laid method of a Plants shell, the performance indications of the carbon-based solid acid that described method prepares need to detect according to applied field, detect qualified after could be used for association area.The carbon-based solid acid that the method for the invention prepares is preferred for the industries such as chemical industry, washing agent, farming and animal husbandry and weaving, does not recommend to be directly used in the fields such as food, medicine, cosmetics.The fields such as food, medicine, cosmetics are applied to as needed carbon-based solid acid the present invention prepared, relevant laws and regulations should be strictly observed, carbon-based solid acid is comprehensively detected, or be further processed, eliminate wherein to the healthy disadvantageous factor of people, these fields could be used for.

Claims (1)

1. a preparation method for carbon-based solid acid, is characterized in that: described carbon-based solid acid utilizes fresh shell District, Xinyang Area, Henan Province chestnut shell to be prepared from for raw material, and obtained carbon-based solid acid specific area is 1127m 2/ g, acid number is 2.48mmol/L,
The concrete steps of described preparation method are,
(1) pretreatment of fresh shell: air-dry fresh shell District, Xinyang Area, Henan Province chestnut shell water is washed till repeatedly and does not have impurity, then the shell of wash clean is put into baking oven dry, remove moisture, the shell that screening product is compared, in disintegrating machine, be crushed to 10 ~ 30 orders for subsequent use;
(2) activation of shell: add 43g activator phosphoric acid in 400mL beaker, 100mL distilled water is poured in beaker, stirring and dissolving obtains activator solution, add through the pretreated fresh shell District, Xinyang Area, Henan Province chestnut shell 30g of step (1) in described activator solution, stir 5min, flood 8h under normal temperature, then the sample flooded is put into 110 DEG C of baking ovens and dry 2h, remove moisture;
(3) carbonization of shell: the shell obtained will be activated in step (2), 450 DEG C are heated under nitrogen protection atmosphere, carbonization 3h, prepare active carbon, by active carbon grind into powder, in the hydrochloric acid solution of 1mol/L, boil 30min, then suction filtration, obtain absorbent charcoal material with after distilled water rinsing, drying;
(4) sulfonation of absorbent charcoal material: by the absorbent charcoal material obtained in step (3), under 130 DEG C of conditions, through oleum sulfonation 8h, the solid-liquid ratio of absorbent charcoal material and sulfonating agent solution is 1:13.5g/mL, mixed liquor after sulfonation is gently poured in cold water and is also constantly stirred, and suction filtration, oven dry gained black solid powder are carbon-based solid acid.
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由生物质木粉制备高比表面积炭基固体酸催化剂的研究;黄苗;《西北农林科技大学硕士学位论文》;20111231;第14-18页第2.5-2.7节以及第20-25页第3.4节 *

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