CN103316695A - Novel integrated solid acid catalyst with carbon-based structure as well as preparation of integrated solid acid catalyst and application in preparation of biodiesel - Google Patents
Novel integrated solid acid catalyst with carbon-based structure as well as preparation of integrated solid acid catalyst and application in preparation of biodiesel Download PDFInfo
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- CN103316695A CN103316695A CN2013102657761A CN201310265776A CN103316695A CN 103316695 A CN103316695 A CN 103316695A CN 2013102657761 A CN2013102657761 A CN 2013102657761A CN 201310265776 A CN201310265776 A CN 201310265776A CN 103316695 A CN103316695 A CN 103316695A
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Abstract
The invention discloses a novel integrated solid acid catalyst with a carbon-based structure. The novel integrated solid acid catalyst is a sulfonating carbon nano tube (CNT-SO3H@) stainless steel material and is prepared by using the stainless steel material as a support material, growing a carbon nano tube on the surface of the support material, vulcanizing through polysulfide and oxidizing. The invention simultaneously discloses a preparation method of the novel catalyst and an application in preparation of biodiesel by means of catalytic distillation. The loss of an acid position of the solid acid catalyst with the carbon-based structure is reduced; because of high heat stability and structure stability, the catalyst is easily made into various shapes and is filled into a catalytic distillation tower to be used. An original element having functions of catalyzing and separating is used for coupling a reaction process with a separation process, and because of the process, the complicated processes of pre-esterification, purification and subsequent separation are avoided; meanwhile, a glycerinum product which is used for catalyzing waste oil and methyl alcohol ester to perform exchange reaction is converted into products of glyceraldehydes, glyceric acid, hexanal dimethyl acetal, acraldehyde dimethyl acetal and the like, so that the reaction is greatly intensified; finally, a biodiesel product with high purity can be directly obtained on the top of the tower and at the bottom of the tower.
Description
Technical field
The present invention relates to a kind of catalyst, particularly a kind of carbon back structural entity catalyst, with and preparation method thereof and application in the preparation biodiesel.
Background technology
Carbon-based solid acid typically refers at carbon material surface and carries out the acidifying modification, introduces acid groups (SO
3H ,-COOH) solid-acid material of prepared one-tenth.Material with carbon element mainly comprise porous carbon, active carbon, carbon fiber, carbon black, carbon microspheres, crystalline flake graphite, glass charcoal, CNT, Graphene, graphite tape, carbon molecular sieve, etc. all polymorphic, wherein more as solid-acid material research at present is porous carbon, CNT and Graphene.The route that acidization is different according to the different choice of material, this research mainly be take CNT as the acidifying object.The acid functionalization mode of bibliographical information mainly contains four kinds, (i) CNT is put into to red fuming nitric acid (RFNA) and concentrated sulfuric acid mixed liquor is boiled; (ii) first in carbon nano tube surface, introduce reactive group, and then replace with sulfydryl, last oxidation obtains the acid position and (iii) by carrying out reacting for a long time with polysulfide, introduces sulfydryl, then through oxidation, obtains the acid position; (iv) adopt sulfurous gas first material to be vulcanized, and then oxidation.The backing material that this research institute uses is stainless steel material, if adopt strong acid and active compound treatment, backing material is difficult to bear, and adopts sulfurous gas to process the element sulphur that can enter the carbon pipe limited, so this research adopts polysulfide to be vulcanized and then this gentle process of oxidation.
The solid acid of carbon back is worked as catalyst, is by the acid of the Bronsted on it position (SO
3H) play catalytic action ,-SO
3H and C have formed covalent bond, and the electron deficient position appears in surface, form electron-withdrawing power and reduce its hydrophily, reduce the loss of sulfonate radical, thereby have avoided the problem of the too fast decline of catalyst activity.
The material with carbon element of above-mentioned use is all powder sample, make carbon-based solid acid after pattern substantially constant.When these powder samples are used as catalysis material, under liquid-phase reaction condition, can mix with reactant, reaction needs isolated by filtration after finishing.And if oil compounds is arranged in reactant, can be adsorbed on catalyst surface, link together, be difficult to filter.Therefore need to be CNT length on stainless steel cloth/sheet, so that separate with grease.
This preparation method of take the carbon back structure solid acid catalyst that CNT is core is at first firmly long on the surface of stainless steel cloth/sheet CNT, and then by gentle condition, CNT is carried out to functionalization.Again this carbon back structure solid catalyst is made to corresponding shape, is packed in packed tower, simultaneously as the catalysis original paper with separate original paper.Because supporting mechanism is stainless steel material, there is good mouldability and thermal conductivity, can make the shape that meets hydrodynamic performance, keep the interior each point temperature of tower even simultaneously.This also have a good heat resistance, it is reported, CNT can be 400
oUnder the C aerobic conditions, continue to use as catalysis material or backing material, therefore can be under relatively high temperature conditions catalytic reaction, greatly improve the efficiency of catalyst.Overcome acid-exchange resin too responsive and be easy to the shortcoming of swelling in organic solvent to temperature.
At ester exchange waste oil, prepare in the biodiesel process, at first need cheap waste grease is carried out to pre-esterification, and to control the water content of raw material, also have follow-up separation concentration process, route is longer, and if adopt carbon back structure solid acid catalyst, without carrying out pre-esterification, itself just can be used as the catalyst of esterification, and simultaneously because directly will react in tower-separation process is coupled together, product is exactly directly high-grade biodiesel.
Existence due to the carbon back structure catalyst, in this reaction, the product glycerine of ester exchange reaction can be further converted to the products such as glyceric acid, glyceraldehyde, hexanal dimethylacetal and methacrylaldehyde dimethylacetal, strengthened ester exchange reaction, also reduced the consumption of methyl alcohol, the part grease also is decomposed into short chain alkanes and flows into tower top under reaction condition, can be used as the biodiesel composition simultaneously, realized that one-step method prepares biodiesel, greatly saved technological process and investment
Carbon back structure solid acid catalyst has enough sour bit densitys, acid strength, little sour bit stream mistake, material structure stability, heat endurance and processability, will open new space for the processing of cheap waste grease and the preparation of biodiesel.
Summary of the invention
The purpose of this invention is to provide a kind of novel carbon back structural entity catalyst that can be applicable to acid catalyzed reaction.
Two of purpose of the present invention is to provide the preparation method of above-mentioned new catalyst.
Three of purpose of the present invention is to provide above-mentioned new catalyst to prepare the application in biodiesel at catalytic distillation.
To achieve these goals, the present invention adopts following technical scheme: a kind of New Type of Carbon based structures integrated solid acid catalyst is CNT-SO
3H@stainless steel material, take stainless steel material as backing material, and the superficial growth CNT vulcanizes then oxidation and makes through polysulfide.
Described stainless steel material is stainless steel cloth or flaky material.
Described polysulfide is many sulphur or many sodium sulfides.
A kind of preparation method of New Type of Carbon based structures integrated solid acid catalyst comprises the following steps:
(1) 1～10g slaine is dissolved in 4～15 mL oleyl amines, then is heated to 100～300
oC, stir and become slurry in 60 minutes, and above-mentioned slurry evenly is coated in to the stainless steel wire material surface; Then sample is put into to tube furnace, under the protection of nitrogen, the flow 30～90mL/min of nitrogen, be warming up to 750 ℃ from room temperature, and keep 3 hours, then uses H
2After reduction 3h, the flow 5mL/min of hydrogen, naturally cool to room temperature, obtains catalyst granules@stainless steel material;
(2) the catalyst granules stainless steel material is put into to tube furnace, metallocene compound is dissolved in to carbon source and with 10～30mL/h injection, enters tube furnace, by 40～90mL/min Ar+5～10mL/min H
2Gas carries the tube furnace center that enters, and at 800 ℃ of catalytic pyrolysis 30～60min, obtains CNTs@stainless steel material;
(3) CNTs@stainless steel wire material is put into to polysulfide solution, at 70～85 ℃ of stirring reaction 12～24h, then take out, with the distilled water washing, at room temperature, with hydroperoxidation 1h, can obtain CNT-SO
3H@stainless steel material.
Described slaine is ferric nitrate, cobalt nitrate or iron chloride etc.Described metallocene compound is ferrocene, dicyclopentadienyl nickel or cobaltocene etc., and described carbon source is the organic compounds such as methyl alcohol, ethanol or benzene.
CNT-SO
3H@stainless steel material prepares the application in biodiesel at catalytic distillation, adopt following steps: described catalyst is made into to given shape, be packed in catalytic distillation tower, waste grease flows in tower from top to bottom by tower top, methyl alcohol at the bottom of tower enters in tower with gas phase after heating, charging oleyl alcohol mol ratio is 1:3～1:12, reflux ratio 0.33～4,70～250 ℃ of reaction temperatures; A product part is under the carrying of methanol stream, flow into tower top, at the bottom of major part flows to tower, the product glycerine of ester exchange reaction is further converted to glyceric acid, glyceraldehyde, hexanal dimethylacetal and methacrylaldehyde dimethylacetal under reaction condition, the short chain alkanes that grease decomposes also flows to tower top, can be used as the biodiesel composition.
Be provided with two step condensations in described catalytic distillation column overhead, first step condensation temperature is set as 90～120 ℃, and the second step condensation temperature is normal temperature.
The filling ratio of described catalyst is 500～2000kg/m
3, make Raschig ring, θ ring, stratiform or netted etc., to interlock, the intensive mode that huddles is loaded.
Set up CNT-SO
3H@stainless steel material prepares the Mathematical Modeling of biodiesel at catalytic distillation tower:
(
).X wherein
D: fatty acid methyl ester is in the molar fraction of liquid phase; L: tower height.
Beneficial effect of the present invention:
(1) CNT is made into to the structure solid acid catalyst, and carrys out catalyzed transesterification with it, for new space has been opened up in the application of CNT.Prepared carbon back structure solid acid catalyst acid bit stream loses few, and heat endurance and structural stability are good, are easy to make various shapes, are packed into catalytic distillation tower and use.
(2) prepared carbon back structure solid acid catalyst is made to specific shape (Raschig ring, the θ ring, stratiform, netted etc.), be packed into catalytic distillation tower, generate the catalyst of biodiesel as the waste grease ester exchange, this original paper that has catalysis and centrifugation concurrently, to react-separation process is coupled together, this process has been avoided loaded down with trivial details pre-esterification, purifying and subsequent separation process, simultaneously can also the catalysis waste oil and the product transformation of glycerol of methyl alcohol ester exchange reaction be glyceraldehyde, glyceric acid, the products such as hexanal dimethylacetal and methacrylaldehyde dimethylacetal, greatly strengthened reaction.Finally can directly at the bottom of tower top, tower, obtain the higher biodiesel product of purity.
(3) carbon back structure solid acid catalyst preparation method novelty of the present invention, be applied to the biodiesel preparation, is initiative technique, and its structure is expected to all waste oil, waste oil are become to well sold and in short supply diesel oil.
The accompanying drawing explanation
Fig. 1 is the Raman spectrogram of the catalyst ion@stainless steel cloth of the embodiment of the present invention 1 preparation.
Fig. 2 is the TEM transmission electron microscope photo of the catalyst ion@stainless steel cloth of the embodiment of the present invention 1 preparation.
Fig. 3 is the SEM stereoscan photograph of the catalyst ion@stainless steel cloth of the embodiment of the present invention 1 preparation.
Fig. 4 is the optical photograph of the CNTs@stainless steel cloth of the embodiment of the present invention 1 preparation.
Fig. 5 is the SEM stereoscan photograph (* 90) of the CNTs@stainless steel cloth of the embodiment of the present invention 1 preparation.
Fig. 6 is the SEM stereoscan photograph (* 1200) of the CNTs@stainless steel cloth of the embodiment of the present invention 1 preparation.
Fig. 7 is the TEM transmission electron microscope photo of the CNTs@stainless steel cloth of the embodiment of the present invention 1 preparation.
Fig. 8 is the CNT-SO of the embodiment of the present invention 1 preparation
3The SEM stereoscan photograph (* 70) of H@stainless steel cloth.
Fig. 9 is the CNT-SO of the embodiment of the present invention 1 preparation
3The TEM transmission electron microscope photo of H@stainless steel cloth.
Figure 10 is the catalytic distillation tower that the embodiment of the present invention 5 preparation biodiesel are used.
Reference numeral wherein: 1-heating jacket; The 2-cooling tube; The 3-liquid conduits; The 4-vapor uptake; 5-magnet; The 6-controller; The 7-needle; The upper sample tap of 8-; Sample tap on 9-second; The 10-return duct; The 11-catalytic distillation tower; The 12-catalytic filler; Sample tap under 13-; The 14-reboiler; The 15-heating jacket; A1-the first thermometer; A2-the second thermometer; A3-the 3rd thermometer; The b1-oil inlet; The import of b2-methyl alcohol.
Figure 11 is the chromatogram result of the biodiesel of the embodiment of the present invention 5 preparations.
Figure 12 is that the interior vapour phase of tower of the embodiment of the present invention 5 preparation biodiesel forms distribution map.
Figure 13 is that the interior liquid phase of tower of the embodiment of the present invention 5 preparation biodiesel forms distribution map.
Figure 14 is the tower internal mold offset of the embodiment of the present invention 5 preparation biodiesel and the comparison diagram of experiment value.
The specific embodiment
Below in conjunction with drawings and Examples, the present invention is further illustrated.
The 5g ferric nitrate is dissolved in 8 mL oleyl amines, then is heated to 180 ℃, stir 60 minutes.Above-mentioned slurry evenly is coated in to the stainless steel wire net surface, then 60 ℃ of lower vacuum drying 24 hours.Then sample is put into to tube furnace, under the protection of nitrogen, (the flow 30mL/min of nitrogen), be warming up to 750 ℃ from room temperature, and keep 3 hours, then uses H
2(the flow 5mL/min of hydrogen) reduces 3h.Afterwards, naturally cool to room temperature, obtain catalyst granules@stainless steel cloth/sheet.The Raman spectrum of product is shown in Fig. 1, and the TEM transmission electron microscope photo is shown in Fig. 2, and the SEM stereoscan photograph is shown in Fig. 3.
Above-mentioned catalyst granules stainless steel cloth is put into to tube furnace, and benzene is as carbon source, and the dicyclopentadienyl nickel mixing is dissolved in wherein, enters tube furnace with the 10mL/h injection, by Ar+H
2(40mL/min+5mL/min) gas carries the tube furnace center that enters, and at 800 ℃ of catalytic pyrolysis 60min, obtains CNTs@stainless steel cloth/sheet.Optical photograph is shown in Fig. 4, and the SEM stereoscan photograph is shown in that Fig. 5 and 6, TEM transmission electron microscope be shown in Fig. 7.
CNTs@stainless steel cloth is put into to many sulphur and acetonitrile solution, at 80 ℃ of stirring reaction 24h, then take out, with the distilled water washing, at room temperature, with hydroperoxidation 1h, can obtain CNT-SO
3H@stainless steel cloth/sheet.The SEM stereoscan photograph is shown in Fig. 8, and the TEM transmission electron microscope photo is shown in Fig. 9.
10g iron chloride is dissolved in the 15mL oleyl amine, then is heated to 300 ℃, stir 60min.Above-mentioned slurry evenly is coated in to stainless steel wire sheet surface, then at 60 ℃ of lower vacuum drying 24h.Then sample is put into to tube furnace, under the protection of nitrogen, (the flow 60mL/min of nitrogen), be warming up to 750 ℃ from room temperature, and keep 3 hours, then uses H
2(the flow 5mL/min of hydrogen) reduces 3h.Afterwards, naturally cool to room temperature, obtain catalyst granules@stainless steel wire sheet.
Above-mentioned catalyst granules stainless steel wire sheet is put into to tube furnace, and ethanol is as carbon source, and the ferrocene mixing is dissolved in wherein, enters tube furnace with the 10mL/h injection, by Ar+H
2(60mL/min+10mL/min) gas carries the tube furnace center that enters, and at 800 ℃ of catalytic pyrolysis 30min, obtains CNTs@stainless steel wire sheet.
CNTs@stainless steel wire sheet is put into to many sodium sulfides solution, at 70 ℃ of stirring reaction 24h, then take out, with the distilled water washing, at room temperature, with hydroperoxidation 1h, can obtain CNT-SO
3H@stainless steel wire sheet.
The 1g cobalt nitrate is dissolved in the 4mL oleyl amine, then is heated to 100 ℃, stir 60 minutes.Above-mentioned slurry evenly is coated in to the stainless steel wire net surface, then 60 ℃ of lower vacuum drying 24 hours.Then sample is put into to tube furnace, under the protection of nitrogen, (the flow 30mL/min of nitrogen), be warming up to 750 ℃ from room temperature, and keep 3 hours, then uses H
2(the flow 5mL/min of hydrogen) reduces 3h.Afterwards, naturally cool to room temperature, obtain catalyst granules@stainless steel cloth.
Above-mentioned catalyst granules stainless steel cloth is put into to tube furnace, and methyl alcohol is as carbon source, and the cobaltocene mixing is dissolved in wherein, enters tube furnace with the 15mL/h injection, by Ar+H
2(90mL/min+5mL/min) gas carries the tube furnace center that enters, and at 800 ℃ of catalytic pyrolysis 40min, obtains CNTs@stainless steel cloth.
CNTs@stainless steel cloth is put into sodium sulfide solution, at 80 ℃ of stirring reaction 24h, then taken out, with the distilled water washing, at room temperature, with hydroperoxidation 1h, can obtain CNT-SO
3H@stainless steel cloth.
Embodiment 4
5g iron chloride is dissolved in 8 mL oleyl amines, then is heated to 200 ℃, stir 60min.Above-mentioned slurry evenly is coated in to the stainless steel wire net surface, then at 60 ℃ of lower vacuum drying 24h.Then sample is put into to tube furnace, under the protection of nitrogen, (the flow 30mL/min of nitrogen), be warming up to 750 ℃ from room temperature, and keep 3 hours, then uses H
2(the flow 5mL/min of hydrogen) reduces 3h.Afterwards, naturally cool to room temperature, obtain catalyst granules@stainless steel cloth.
Above-mentioned catalyst granules stainless steel cloth is put into to tube furnace, and benzene is as carbon source, and the dicyclopentadienyl nickel mixing is dissolved in wherein, enters tube furnace with the 10mL/h injection, by Ar+H
2(40mL/min+5mL/min) gas carries the tube furnace center that enters, and at 800 ℃ of catalytic pyrolysis 60min, obtains CNTs@stainless steel cloth.
CNTs@stainless steel cloth is put into to many sulphur and acetonitrile solution, at 80 ℃ of stirring reaction 24h, then take out, with the distilled water washing, at room temperature, with hydroperoxidation 1h, can obtain CNT-SO
3H@stainless steel cloth.
Embodiment 5
By the CNT-SO obtained in embodiment 1
3H@stainless steel cloth is made into given shape: Raschig ring, θ ring, stratiform, netted etc., be packed in the catalytic distillation tower (see figure 10), and the filling ratio is 2000kg/m
3Waste grease flows in tower from top to bottom by tower top, methyl alcohol at the bottom of tower enters in tower with gas phase after heating, flow mol ratio (oleyl alcohol ratio) is 1:7, reflux ratio 4,250 ℃ of reaction temperatures, in course of reaction, glycerine synchronously is converted into the products such as glyceraldehyde, glyceric acid, hexanal dimethylacetal and methacrylaldehyde dimethylacetal, the strengthening ester exchange reaction.In tower, after reaction, the biodiesel product streams such as methyl hexadecanoate are at the bottom of tower top and tower, and the short chain alkanes that other grease decomposes also flows to tower top, can be used as the biodiesel composition.Be provided with two step condensations at tower top, first step condensation temperature is set as 120
oC, the fatty acid methyl ester in product is condensed, takes out in this step, and methyl alcohol, a small amount of water and other short chain alkanes enter next step condensation, the second step condensation temperature is normal temperature.Finally can at the bottom of tower top, tower, obtain the biodiesel product that purity is higher.The gas chromatography-mass spectrometry chromatogram of product is shown in Figure 11, wherein: 4-methyl hexadecanoate CH
3(CH
2)
14COOCH
35-methyl linoleate CH
3(CH2)
4CH=CHCH
2CH=CH (CH
2)
7COOCH
36-methyl oleate CH
3(CH
2)
7CH=CH (CH
2)
7COOCH
37-methyl stearate CH
3(CH
2)
16COOCH
3.
According to the experiment structure, set up and be applicable to the Mathematical Modeling that this catalytic distillation tower prepares biodiesel:
(
).Wherein
X D : fatty acid methyl ester is in the molar fraction of liquid phase;
l: tower height.The distribution of product each section in tower and the comparing result of model value and experiment value are shown in respectively Figure 12,13 and 14.
Embodiment 6
By the CNT-SO obtained in embodiment 1
3H@stainless steel cloth is made into given shape: Raschig ring, θ ring, stratiform, netted etc., be packed in catalytic distillation tower, and the filling ratio is 500kg/m
3Waste grease flows in tower from top to bottom by tower top, methyl alcohol at the bottom of tower enters in tower with gas phase after heating, flow mol ratio (oleyl alcohol ratio) is 1:12, reflux ratio 0.33,120 ℃ of reaction temperatures, after reacting in tower, the biodiesel product streams such as methyl hexadecanoate are at the bottom of tower top and tower, and glycerine is converted into the products such as glyceric acid, glyceraldehyde, hexanal dimethylacetal and methacrylaldehyde dimethylacetal under the catalysis of carbon back structure catalyst, the strengthening ester exchange reaction.In tower, after reaction, the biodiesel product streams such as methyl hexadecanoate are at the bottom of tower top and tower, and the short chain alkanes that other grease decomposes also flows to tower top, can be used as the biodiesel composition.Be provided with two step condensations at tower top, first step condensation temperature is set as 90
oC, the fatty acid methyl ester in product is condensed, takes out in this step, and methyl alcohol, a small amount of water and other short chain alkanes enter next step condensation, the second step condensation temperature is normal temperature.Finally can at the bottom of tower top, tower, obtain the biodiesel product that purity is higher.
Embodiment 7
By the CNT-SO obtained in embodiment 1
3H@stainless steel cloth is made into given shape: Raschig ring, θ ring, stratiform, netted etc., be packed in catalytic distillation tower, and the filling ratio is 1200kg/m
3Waste grease flows in tower from top to bottom by tower top, methyl alcohol at the bottom of tower enters in tower with gas phase after heating, flow mol ratio (oleyl alcohol ratio) is 1:3, reflux ratio 2.1,150 ℃ of reaction temperatures, after reacting in tower, the biodiesel product streams such as methyl hexadecanoate are at the bottom of tower top and tower, and glycerine is converted into the products such as glyceric acid, glyceraldehyde, hexanal dimethylacetal and methacrylaldehyde dimethylacetal under the catalysis of carbon back structure catalyst, the strengthening ester exchange reaction.In tower, after reaction, the biodiesel product streams such as methyl hexadecanoate are at the bottom of tower top and tower, and the short chain alkanes that other grease decomposes also flows to tower top, can be used as the biodiesel composition.Be provided with two step condensations at tower top, first step condensation temperature is set as 100
oC, the fatty acid methyl ester in product is condensed, takes out in this step, and methyl alcohol, a small amount of water and other short chain alkanes enter next step condensation, the second step condensation temperature is normal temperature.Finally can at the bottom of tower top, tower, obtain the biodiesel product that purity is higher.
Although the present invention with preferred embodiment openly as above; but embodiment and accompanying drawing are not for limiting the present invention, anyly be familiar with this skill person, without departing from the spirit and scope of the invention; from working as, can make various changes or retouch, but equally within protection scope of the present invention.What therefore protection scope of the present invention should be defined with the application's claim protection domain is as the criterion.
Claims (10)
1. a New Type of Carbon based structures integrated solid acid catalyst, it is characterized in that: described catalyst is CNT-SO
3H@stainless steel material, take stainless steel material as backing material, and the superficial growth CNT vulcanizes then oxidation and makes through polysulfide.
2. New Type of Carbon based structures integrated solid acid catalyst according to claim 1, it is characterized in that: described stainless steel material is stainless steel cloth or flaky material.
3. New Type of Carbon based structures integrated solid acid catalyst according to claim 1, it is characterized in that: described polysulfide is many sulphur or many sodium sulfides.
4. the preparation method of New Type of Carbon based structures integrated solid acid catalyst according to claim 1 is characterized in that comprising the following steps:
(1) 1～10g slaine is dissolved in 4～15 mL oleyl amines, then is heated to 100～300
oC, stir and become slurry in 60 minutes, above-mentioned slurry evenly is coated in to the stainless steel wire material surface, 60 ℃ of lower vacuum drying 24 hours; Then sample is put into to tube furnace, under the protection of nitrogen, the flow 30～90mL/min of nitrogen, be warming up to 750 ℃ from room temperature, and keep 3 hours, then uses H
2After reduction 3h, the flow 5mL/min of hydrogen, naturally cool to room temperature, obtains catalyst granules@stainless steel material;
(2) the catalyst granules stainless steel material is put into to tube furnace, metallocene compound is dissolved in to carbon source and with 10～30mL/h injection, enters tube furnace, by 40～90mL/min Ar+5～10mL/min H
2Gas carries the tube furnace center that enters, and at 800 ℃ of catalytic pyrolysis 30～60min, obtains CNTs@stainless steel material;
(3) CNTs@stainless steel wire material is put into to polysulfide solution, at 70～85 ℃ of stirring reaction 12～24h, then take out, with the distilled water washing, at room temperature, with hydroperoxidation 1h, can obtain CNT-SO
3H@stainless steel material.
5. the preparation method of New Type of Carbon based structures integrated solid acid catalyst according to claim 4, it is characterized in that: described slaine is ferric nitrate, cobalt nitrate or iron chloride.
6. the preparation method of New Type of Carbon based structures integrated solid acid catalyst according to claim 4, it is characterized in that: described metallocene compound is ferrocene, dicyclopentadienyl nickel or cobaltocene, described carbon source is methyl alcohol, ethanol or benzene.
7. CNT-SO according to claim 1
3H@stainless steel material prepares the application in biodiesel at catalytic distillation, it is characterized in that: described catalyst is made into to given shape, be packed in catalytic distillation tower, waste grease flows in tower from top to bottom by tower top, methyl alcohol at the bottom of tower enters in tower with gas phase after heating, charging oleyl alcohol mol ratio is 1:3～1:12, reflux ratio 0.33～4,70～250 ℃ of reaction temperatures; A product part is under the carrying of methanol stream, flow into tower top, at the bottom of major part flows to tower, the product glycerine of ester exchange reaction is further converted to glyceric acid, glyceraldehyde, hexanal dimethylacetal and methacrylaldehyde dimethylacetal under reaction condition, the short chain alkanes that grease decomposes also flows to tower top, can be used as the biodiesel composition.
8. CNT-SO according to claim 7
3The H stainless steel material prepares the application in biodiesel at catalytic distillation, it is characterized in that: be provided with two step condensations in described catalytic distillation column overhead, first step condensation temperature is set as 90～120 ℃, and the second step condensation temperature is normal temperature.
9. CNT-SO according to claim 7
3H@stainless steel material prepares the application in biodiesel at catalytic distillation, it is characterized in that: the filling ratio of described catalyst is 500～2000kg/m
3, make Raschig ring, θ ring, stratiform or netted, to interlock, the intensive mode that huddles is loaded.
10. CNT-SO according to claim 7
3H@stainless steel material prepares the application in biodiesel at catalytic distillation, it is characterized in that: set up CNT-SO
3H@stainless steel material prepares the Mathematical Modeling of biodiesel at catalytic distillation tower:
(
), wherein
X D : fatty acid methyl ester is in the molar fraction of liquid phase;
l: tower height.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103725424A (en) * | 2014-01-23 | 2014-04-16 | 湖南未名创林生物能源有限公司 | Method for producing biodiesel |
| CN105728001A (en) * | 2016-02-26 | 2016-07-06 | 江西理工大学 | Catalyst as well as preparation method and application thereof |
| CN115611707A (en) * | 2022-09-30 | 2023-01-17 | 上海中器环保科技有限公司 | Purification process of biodiesel byproduct crude glycerol |
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| US20060124028A1 (en) * | 2004-12-09 | 2006-06-15 | Xueying Huang | Inkjet ink compositions comprising carbon nanotubes |
| CN102671687A (en) * | 2012-06-07 | 2012-09-19 | 上海第二工业大学 | Composite metal nitrogen-doped carbon nanotube catalyst, preparation method thereof and method for catalyzing biodiesel by utilizing catalyst |
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| US20060124028A1 (en) * | 2004-12-09 | 2006-06-15 | Xueying Huang | Inkjet ink compositions comprising carbon nanotubes |
| CN102671687A (en) * | 2012-06-07 | 2012-09-19 | 上海第二工业大学 | Composite metal nitrogen-doped carbon nanotube catalyst, preparation method thereof and method for catalyzing biodiesel by utilizing catalyst |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103725424A (en) * | 2014-01-23 | 2014-04-16 | 湖南未名创林生物能源有限公司 | Method for producing biodiesel |
| CN105728001A (en) * | 2016-02-26 | 2016-07-06 | 江西理工大学 | Catalyst as well as preparation method and application thereof |
| CN105728001B (en) * | 2016-02-26 | 2019-02-22 | 江西理工大学 | A kind of catalyst and its preparation method and application |
| CN115611707A (en) * | 2022-09-30 | 2023-01-17 | 上海中器环保科技有限公司 | Purification process of biodiesel byproduct crude glycerol |
| CN115611707B (en) * | 2022-09-30 | 2024-01-02 | 上海中器环保科技有限公司 | Process for purifying biodiesel byproduct crude glycerine |
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