CN108927218A - A kind of polyaniline-coated biology carbon material and its preparing the application in solid base - Google Patents

A kind of polyaniline-coated biology carbon material and its preparing the application in solid base Download PDF

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Publication number
CN108927218A
CN108927218A CN201810743453.1A CN201810743453A CN108927218A CN 108927218 A CN108927218 A CN 108927218A CN 201810743453 A CN201810743453 A CN 201810743453A CN 108927218 A CN108927218 A CN 108927218A
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polyaniline
carbon material
coated
hours
coated biology
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Inventor
葛本
毛楚畅
罗志臣
岳金方
韦玲
戴凯麒
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Yangzhou Polytechnic Institute
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Yangzhou Polytechnic Institute
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J35/396
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/03Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/02Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11CFATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/04Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C11C3/10Ester interchange
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40Substitution 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
    • B01J2231/49Esterification or transesterification

Abstract

The present invention relates to a kind of polyaniline-coated biology carbon material and its preparing the application in solid base; the preparation method of the polyaniline-coated biology carbon material includes the following steps: that (1) takes dry sweet potato leaves; under nitrogen protection; it is warming up to 600-700 degree; after carbonization 5-6 hours; cooled to room temperature obtains biological carbon material;(2) after the biological carbon material hydrochloric acid solution ultrasound for obtaining step (1) is impregnated 4-5 hours, aniline is added, under ice bath, ammonium persulfate solution is added, 6-10h is reacted in continuation under ice bath, and filtering, washing of precipitate are drying to obtain polyaniline-coated biology carbon material.

Description

A kind of polyaniline-coated biology carbon material and its preparing the application in solid base
Technical field
The invention belongs to biodiesel catalyst fields, and in particular to a kind of polyaniline-coated biology carbon material and its make Application in standby solid base.
Background technique
Biodiesel becomes the hot spot of various countries' research because of its environment friendly, reproducibility.Biodiesel is with vegetable oil, dynamic Object fat oil, waste cooking oils etc. are raw material, carry out transesterification with the alcohol of low molecular weight respectively and fatty acid alkyl monoesters are made, Property is very close with mineral diesel, is a kind of reproducible clean fuel.Although the method for existing many preparation biodiesel, But large-scale industrial production, it still uses based on the homogeneous catalysis such as traditional liquid acid, alkali, common homogeneous catalyst has CaO、H2SO4, NaOH etc., severe corrosion to equipment, and product need to carry out neutralization washing, so as to cause a large amount of industrial wastewaters It generates, causes environmental pollution.The present invention provides a kind of polyaniline-coated biology carbon material supported solid base catalyst, can be with Efficiently preparation biodiesel, has the characteristics that reaction condition is mild, easily separated, reusable.
Summary of the invention
The present invention provides a kind of polyaniline-coated biology carbon material, it is characterised in that the polyaniline-coated biology carbon material Preparation method include the following steps:
(1) dry sweet potato leaves are taken, under nitrogen protection, are warming up to 600-700 degree, after carbonization 5-6 hours, natural cooling To room temperature, biological carbon material is obtained;
(2) after the biological carbon material hydrochloric acid solution ultrasound for obtaining step (1) is impregnated 4-5 hours, aniline, ice bath is added Under, ammonium persulfate solution is added, 6-10h is reacted in continuation under ice bath, and filtering, washing of precipitate are drying to obtain polyaniline-coated life Object carbon material.
The preferred 1.0-2.0mol/L of concentration of hydrochloric acid described in step (2), every gram of biological carbon materials'use 10-15mL hydrochloric acid Solution, every gram of biological carbon materials'use aniline 0.5mL, every milliliter of aniline use 10-15mmol ammonium persulfate, the ammonium persulfate The preferred 0.5-1.0mol/L of the concentration of solution;Supersonic frequency is 30-40kHz.
Another embodiment of the present invention provides application of the above-mentioned polyaniline-coated biology carbon material in load alkali.
Another embodiment of the present invention provides a kind of polyaniline-coated biology carbon material supported alkali, it is characterised in that described The preparation method of the carbon material supported alkali of polyaniline-coated biology includes the following steps:
(1) dry sweet potato leaves are taken, under nitrogen protection, are warming up to 600-700 degree, after carbonization 5-6 hours, natural cooling To room temperature, biological carbon material is obtained;
(2) after the biological carbon material hydrochloric acid solution ultrasound for obtaining step (1) is impregnated 4-5 hours, aniline, ice bath is added Under, ammonium persulfate solution is added, 6-10h is reacted in continuation under ice bath, and filtering, washing of precipitate are drying to obtain polyaniline-coated life Object carbon material.
(3) the polyaniline-coated biology carbon material for obtaining step (2) and KF, K2CO3After mixing and ball milling 6 hours, successively use Water, dehydrated alcohol washing, be dried in vacuo under the conditions of 90 DEG C be dried in vacuo for 24 hours up to polyaniline-coated biology it is carbon material supported Alkali.
The preferred 1.0-2.0mol/L of concentration of hydrochloric acid described in step (2), every gram of biological carbon materials'use 10-15mL hydrochloric acid Solution, every gram of biological carbon materials'use aniline 0.5mL, every milliliter of aniline use 10-15mmol ammonium persulfate, the ammonium persulfate The preferred 0.5-1.0mol/L of the concentration of solution;Supersonic frequency is 30-40kHz.
Polyaniline-coated biology carbon material, KF, K in step (3)2CO3Mass ratio be 1:1:3.
It is anti-in catalytic transesterification that another embodiment of the present invention provides the carbon material supported alkali of above-mentioned polyaniline-coated biology Application in answering.
Another embodiment of the present invention provides the carbon material supported alkali of above-mentioned polyaniline-coated biology in preparation biodiesel In application.
Another embodiment of the present invention provides a kind of preparation method of biodiesel, it is characterised in that including walking as follows It is rapid:
(1) the deacidification processing of grease: suitable sodium hydrate aqueous solution is added into grease, after stirring 0.5-1.0h, turns Enter in separatory funnel, stratification, collect supernatant liquid, after 50-60 DEG C of water washing to neutrality, be added hexamethylene, with point Hydrophone removes extra moisture, and finally vacuum distillation removes hexamethylene to get acid lipid is removed;
(2) after acid lipid, methanol, catalyst mixing being removed obtained in step (1), 60-65 DEG C is heated under stirring, instead After answering 3-4 hours, filtering or centrifugation recycling catalyst, remaining reaction solution is after being evaporated off methanol, stratification, on Layer liquid is biodiesel, and lower layer is glycerol.
The preferred soybean oil of grease, palm oil, peanut oil, rapeseed oil or gutter oil described in step (1);Sodium hydroxide is water-soluble The concentration of liquid is 0.2-0.3mol/L, and the volume ratio of grease and sodium hydrate aqueous solution is 4:1;The preferred grease body of hexamethylene volume Long-pending 1/3-1/4;
Catalyst described in step (2) is selected from the carbon material supported alkali of the above-mentioned polyaniline-coated biology of the present invention, and dosage is The 0.5-0.8% of deacidification oil quality, except the mass ratio of acid lipid and methanol is 1:8-10.
Another embodiment of the present invention provides the carbon material supported alkali of above-mentioned polyaniline-coated biology and is preparing fatty acid methyl Application in ester.
Another embodiment of the present invention provides a kind of preparation method of fatty acid methyl ester, it is characterised in that including walking as follows It is rapid:
After fatty acid glycerine fat, methanol, catalyst are mixed, after 60-65 DEG C, reaction 3-4 hours is heated under stirring, mistake Filter or centrifugation recycling catalyst, remaining reaction solution is after being evaporated off methanol, stratification, and supernatant liquid is fat Sour methyl esters, lower layer are glycerol.
The catalyst is selected from the carbon material supported alkali of the above-mentioned polyaniline-coated biology of the present invention, and dosage is fatty acid glycerine The mass ratio of the 0.5-0.8% of lipid amount, fatty acid glycerine fat and methanol is 1:8-10.
The preferred C16-C20 of the carbon chain lengths of fatty acid, fatty acid glycerine fat are further preferred in the fatty acid glycerine fat Olein, tripalmitin;The olein is glyceryl monooleate, double oleins or three oleics The mixing of one or more of ester;The tripalmitin is monopalmitin, double tripalmitins or three palms The mixing of one or more of acid glyceride.
Compared with the prior art, the advantages of the present invention are as follows: (1) present invention by the method for ball milling keep polyaniline-coated raw Object carbon material supported KF, K2CO3, a kind of novel solid body base is obtained, the solid base energy efficient catalytic grease (including fatty acid glycerine Ester) and methanol between occur ester exchange reaction, prepare biodiesel;(2) polyaniline-coated biology of the present invention is carbon material supported Base catalysis is high-efficient, easily separated, and can be recycled, and using 6 times, catalytic activity is basically unchanged.
Detailed description of the invention
Fig. 1 is nitrogen adsorption-desorption isotherm figure of product a;
Fig. 2 is the SEM figure of product A;
Fig. 3 is the SEM figure of product G.
Specific embodiment
For the ease of a further understanding of the present invention, examples provided below has done more detailed description to it.But It is that these embodiments are only not supposed to be a limitation to the present invention or implementation principle for better understanding invention, reality of the invention The mode of applying is not limited to the following contents.
Embodiment 1
(1) dry sweet potato leaves (400g) is taken, under nitrogen protection, after being warming up to 600 degree, carbonization 6 hours, natural cooling To room temperature, biological carbon material is obtained;
(2) the biological carbon material (10g) for taking step (1) to obtain hydrochloric acid solution (1.0mol/L, 150mL) ultrasound It after (30kHz) impregnates 5 hours, is added aniline (5mL), under ice bath, is added ammonium persulfate solution (0.5mol/L, 100mL), continues 10h is reacted under ice bath, filtering, washing of precipitate are drying to obtain polyaniline-coated biology carbon material (hereinafter referred to as product a).
Embodiment 2
(1) dry sweet potato leaves (400g) is taken, under nitrogen protection, after being warming up to 700 degree, carbonization 5 hours, natural cooling To room temperature, biological carbon material is obtained;
(2) the biological carbon material (10g) for taking step (1) to obtain hydrochloric acid solution (2.0mol/L, 100mL) ultrasound It after (40kHz) impregnates 4 hours, is added aniline (5mL), under ice bath, is added ammonium persulfate solution (1.0mol/L, 75mL), continues 6h is reacted under ice bath, filtering, washing of precipitate are drying to obtain polyaniline-coated biology carbon material (hereinafter referred to as product b).
Embodiment 3
Take product a (4g) and KF (4g), K2CO3(12g) mixing and ball milling is successively washed with water, dehydrated alcohol after 6 hours, in It is dried in vacuo and is dried in vacuo for 24 hours up to the carbon material supported alkali (hereinafter referred to as product A) of polyaniline-coated biology under the conditions of 90 DEG C.
Embodiment 4
Take product b (3g) and KF (3g), K2CO3(9g) mixing and ball milling is successively washed with water, dehydrated alcohol after 6 hours, in It is dried in vacuo and is dried in vacuo for 24 hours up to the carbon material supported alkali (hereinafter referred to as product B) of polyaniline-coated biology under the conditions of 90 DEG C.
Embodiment 5
It takes product a (4g) and KF (4g) after mixing and ball milling 6 hours, is successively washed with water, dehydrated alcohol, under the conditions of 90 DEG C Vacuum drying is dried in vacuo to obtain the carbon material supported alkali (hereinafter referred to as products C) of polyaniline-coated biology for 24 hours.
Embodiment 6
Take product a (4g) and K2CO3(12g) mixing and ball milling is successively washed with water, dehydrated alcohol after 6 hours, in 90 DEG C of items It is dried in vacuo under part and is dried in vacuo to obtain the carbon material supported alkali (hereinafter referred to as product D) of polyaniline-coated biology for 24 hours.
Embodiment 7
Take product a (4g) and KF (4g), K2CO3(4g) mixing and ball milling is successively washed with water, dehydrated alcohol after 6 hours, in It is dried in vacuo under the conditions of 90 DEG C and is dried in vacuo to obtain the carbon material supported alkali (hereinafter referred to as product E) of polyaniline-coated biology for 24 hours.
Embodiment 8
The biological carbon material (4g) and KF (4g), K of 1 step of Example (1) preparation2CO3(12g) mixing and ball milling 6 hours Afterwards, successively washed with water, dehydrated alcohol, be dried in vacuo under the conditions of 90 DEG C be dried in vacuo for 24 hours biological carbon material supported alkali (with Lower abbreviation product F).
Embodiment 9
Product a (4g) is taken to be added containing KF (4g), K2CO3In the aqueous solution (200mL) of (12g), after stirring 24 hours, filtering, Precipitating is successively washed with water, dehydrated alcohol, is dried in vacuo under the conditions of 90 DEG C and is dried in vacuo to obtain polyaniline-coated biology carbon materials for 24 hours Material load alkali (hereinafter referred to as product G).
Embodiment 10
(1) it the deacidification processing of grease: takes soybean oil (60mL) that sodium hydrate aqueous solution (0.2mol/L, 15mL) is added, stirs It after mixing 1.0h, is transferred in separatory funnel, stratification, collects supernatant liquid, after 50-55 DEG C of water washing to neutrality, be added Hexamethylene (20mL), extra moisture is removed with water segregator, and finally vacuum distillation removes hexamethylene to get deacidification soybean oil;
(2) it after taking deacidification soybean oil (20g), methanol (160g) obtained in step (1), product A (160mg) to mix, stirs It mixes down after being heated to 65 DEG C, reaction 3 hours, centrifugation recycling product A, remaining reaction solution is quiet after methanol is evaporated off Layering is set, supernatant liquid is biodiesel (faint yellow), and lower layer is glycerol;Pass through gas Chromatographic Determination, the production of biodiesel Rate is 96.3%.
According to the method for step (2), the product A of 5 recycling is recycled, catalytic activity is basically unchanged, the 6th secondary pollutant The yield of diesel oil remains to reach 91.0%.
Embodiment 11
(1) it the deacidification processing of grease: takes gutter oil (100mL) that sodium hydrate aqueous solution (0.3mol/L, 25mL) is added, stirs It after mixing 0.5h, is transferred in separatory funnel, stratification, collects supernatant liquid, after 55-60 DEG C of water washing to neutrality, be added Hexamethylene (25mL), extra moisture is removed with water segregator, and finally vacuum distillation removes hexamethylene to get deacidification gutter oil;
(2) it after taking deacidification gutter oil (20g), methanol (200g) obtained in step (1), product B (100mg) to mix, stirs It mixes down after being heated to 60 DEG C, reaction 4 hours, centrifugation recycling product B, remaining reaction solution is quiet after methanol is evaporated off Layering is set, supernatant liquid is biodiesel (faint yellow), and lower layer is glycerol;Pass through gas Chromatographic Determination, the production of biodiesel Rate is 94.3%;It is recycled the product B of recycling, the yield of the 6th secondary pollutant diesel oil is up to 89.8%.
Embodiment 12
According to the operation in 10 step of embodiment (2), respectively with etc. quality product B-G substitute products A, biodiesel Yield see the table below.
Catalyst Biodiesel production rate
Product B 94.7%
Products C 12.5%
Product D 37.3%
Product E 63.1%
Product F 42.6%
Product G 47.2%
Embodiment 13
After taking olein (10g), methanol (80g), product A (80mg) to mix, 65 DEG C are heated under stirring, reaction After 3 hours, centrifugation recycling product A, remaining reaction solution is after being evaporated off methanol, stratification, and supernatant liquid is Biodiesel (faint yellow), lower layer are glycerol;By gas Chromatographic Determination, the yield of biodiesel is 95.6%.
Embodiment 14
After taking tripalmitin (10g), methanol (100g), product A (50mg) to mix, 60 DEG C are heated under stirring, After reaction 4 hours, centrifugation recycling product B, remaining reaction solution is after being evaporated off methanol, stratification, supernatant liquid As biodiesel (faint yellow), lower layer are glycerol;By gas Chromatographic Determination, the yield of biodiesel is 92.2%.

Claims (7)

1. a kind of polyaniline-coated biology carbon material, it is characterised in that the preparation method packet of the polyaniline-coated biology carbon material Include following steps:
(1) dry sweet potato leaves are taken, under nitrogen protection, 600-700 degree is warming up to and naturally cools to room after carbonization 5-6 hours Temperature obtains biological carbon material;
(2) after the biological carbon material hydrochloric acid solution ultrasound obtained step (1) is impregnated 4-5 hour, addition aniline, under ice bath, Ammonium persulfate solution is added, 6-10h is reacted in continuation under ice bath, and filtering, is drying to obtain polyaniline-coated biological carbon at washing of precipitate Material.
2. polyaniline-coated biology carbon material described in claim 1, it is characterised in that the concentration of hydrochloric acid described in step (2) is excellent Select 1.0-2.0mol/L, every gram of biological carbon materials'use 10-15mL hydrochloric acid solution, every gram of biological carbon materials'use aniline 0.5mL, Every milliliter of aniline uses 10-15mmol ammonium persulfate.
3. the described in any item polyaniline-coated biology carbon materials of claim 1-2, it is characterised in that over cure described in step (2) The preferred 0.5-1.0mol/L of the concentration of acid ammonium solution.
4. the described in any item polyaniline-coated biology carbon materials of claim 1-3, it is characterised in that supersonic frequency in step (2) For 30-40kHz.
5. the preparation method of the described in any item polyaniline-coated biology carbon materials of claim 1-4.
6. application of the described in any item polyaniline-coated biology carbon materials of claim 1-4 in load alkali.
7. application as claimed in claim 6, it is characterised in that the described in any item polyaniline-coated biology carbon materials of claim 1-4 Material and KF, K2CO3It after mixing and ball milling 6 hours, is successively washed with water, dehydrated alcohol, vacuum for 24 hours is dried in vacuo under the conditions of 90 DEG C It is drying to obtain the carbon material supported alkali of polyaniline-coated biology.
CN201810743453.1A 2018-07-06 2018-07-06 A kind of polyaniline-coated biology carbon material and its preparing the application in solid base Pending CN108927218A (en)

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