CN101735371B - Hydroxyl type anion resin containing imidazole structure, method for preparing same and application thereof in preparation of biodiesel - Google Patents
Hydroxyl type anion resin containing imidazole structure, method for preparing same and application thereof in preparation of biodiesel Download PDFInfo
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- CN101735371B CN101735371B CN2009102179778A CN200910217977A CN101735371B CN 101735371 B CN101735371 B CN 101735371B CN 2009102179778 A CN2009102179778 A CN 2009102179778A CN 200910217977 A CN200910217977 A CN 200910217977A CN 101735371 B CN101735371 B CN 101735371B
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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Abstract
The invention relates to hydroxyl type anion resin containing an imidazole structure, a method for preparing the same and application thereof in the preparation of biodiesel. The hydroxyl type anion resin containing the imidazole structure is characterized by has a structural formula below. The hydroxyl type anion resin containing the imidazole structure, provided by the invention, can be used as a catalyst for the preparation of the biodiesel; the catalyst solves the problem of difficult recovery of ionic liquid and can be recovered by simple filtration; the catalyst can be regenerated for cycle use; after the catalyst is recycled, the catalytic activity of the catalyst is stable, and after the catalyst is recovered for three times, the conversion rate of the biodiesel is 90 percent, so that the catalyst is the more ideal catalyst for preparing the biodiesel; and when the catalyst is used for preparing the biodiesel, the common equipment is used, the reaction temperature is only between 40 and 60 DEG C, the reaction conditions are mild, and the energy consumption is saved.
Description
Technical field
The present invention relates to contain hydroxyl type anion resin and the method for making of glyoxaline structure and in the application of preparation biofuel.
Background technology
Growing along with the exhausted day by day and energy demand of global petroleum resources, and the problems such as environmental pollution that cause of oil fuel, the renewable energy source of developing the non-petroleum-type of environmental protection is a future source of energy main body of development thinking.Biofuel has caused the great attention of countries in the world owing to have the advantage of renewable, the feature of environmental protection, alternative existing oil fuel, becomes most popular petroleum-type substitute products.
At present the industrial production of biofuel mainly is to be raw material with soya-bean oil, rapeseed oil, peanut oil, plam oil, Oleum Gossypii semen and animal oil and fat, useless food and drink wet goods; Carry out transesterification reaction with methyl alcohol under certain condition; Glycerine in the tri-glyceride in the raw material is replaced to get off, generate longer chain fatty acid methyl esters class material.Traditional chemical method adopts strong acid (like sulfuric acid etc.) or highly basic (like sodium hydroxid or Pottasium Hydroxide etc.) as catalyzer usually, though the catalyzer low price that this method is used, reaction conditions is gentle relatively; Speed of reaction is fast; But these catalyzer have severe corrosive, are difficult for Separation and Recovery after the reaction, need to product neutralize, subsequent disposal such as washing; Make technical process complicacy and production cost increase, it is big for environment pollution to produce a large amount of waste water and waste residue simultaneously.Therefore the friendly catalyzer of development environment becomes the gordian technique in the production biofuel process.
Solid catalyst has active high, and selectivity reaches reaction conditions gentleness and advantages such as product is easy to separate well.But conventional superpower solid alkali prepares complicacy mostly, and cost is expensive, and intensity is relatively poor, very easily by the CO in the atmosphere
2, H
2Contaminating impurities such as O.Ion exchange resin is divided into anionite-exchange resin and Zeo-karb, and anionite-exchange resin all is better than Zeo-karb from reaction mechanism and catalytic activity.The anionite-exchange resin of report has PA306s (N.S.Kitakawa, H.Honda, H.Kuribayashi, T.Toda, Bioresour.Technol.2007 at present; 98,416-421), Marathon MSA (M.Kim, S.O.Salley, K.Y.S.Ng; EnergyFuels.2008,22,3594-3599), A26 (Y.J.Liu; E.Lotero, J.G.Goodwin Jr., C.Q.Lu, J.Catal.2007; 246,428-433) etc., wherein be that matrix is more with the styrene-divinylbenzene copolymer, binding groups is a quaternary ammonium salt.PA306s has bigger specific surface area, thereby its better catalytic activity, but because it can not provide competent basic sites, react after two hours productive rate and obviously do not improve, and is that the resin physical strength of matrix is relatively poor, easy crisp with the PS.And Marahon MSA and A26 to the katalysis of transesterification reaction all a little less than, the quaternary ammonium salt cationic group is unstable at alkaline environment, catalytic activity is prone to inactivation.
Ionic liquid is made up of organic cation and inorganic or organic anion; The salt that under near temperature room temperature or the room temperature, is in a liquid state; Ionic liquid has high-density reaction active site and solid acid non-volatile of liquid acid simultaneously; Structure and acid adjustability, good heat-staple advantage, so ionic liquid is called as a kind of novel eco-friendly green solvent and liquid acid catalyst.Wu Qin etc. (Q.Wu, H.Chen, M.han, Ind.Eng.Chem.Res.2007,46,7955-7960) utilize band-SO
3The B acid ion liquid catalyst Oleum Gossypii semen transesterification reaction of H functional group prepares biofuel, and the result shows that sulfonic acid class B acid ion liquid has good catalytic activity, and its catalytic activity is relevant with nitrogen-containing functional group and carbon chain lengths in the positively charged ion.The method of acidity such as alkyl imidazole, alkyl pyridine, quaternary ammonium salt or alkali ionic liquid catalysis for preparing biodiesel oil is disclosed among the Chinese patent CN1696248A.Above-mentioned ionic liquid acid catalysis prepares in the process of biofuel and exists ionic liquid and by-product glycerin not easily separated; And the viscosity of glycerine and fusing point are all very high; Increased the separating difficulty of ionic liquid and glycerine, because ion liquid price is higher, therefore industry is promoted and is restricted.
Summary of the invention
In order to overcome the shortcoming of above-mentioned ion liquid system, can the mode through covalent linkage such as ionic liquid cationic moiety such as imidazoles functional group, pyridine functional groups etc. be fixed on the polymer carrier, prepare the novel anionic exchange resin.The strong base anion resins that contains glyoxaline structure of the present invention's preparation has higher specific surface area and satisfactory stability property; In the catalysis for preparing biodiesel oil process, has higher catalytic performance; Work out a kind of eco-friendly biodiesel catalyst efficient and with low cost and novel preparation method, be expected to be applied to suitability for industrialized production.
The purpose of this invention is to provide the hydroxyl type anion resin that contains glyoxaline structure and method for making and in the application of preparation biofuel.
The hydroxyl type anion resin that contains glyoxaline structure provided by the invention, its structural formula is following:
The physico-chemical property of hydroxyl type anion resin that contains glyoxaline structure is following:
The preparation principle that contains the hydroxyl type anion resin of glyoxaline structure provided by the invention is:
PS-DVB is the styrene-divinylbenzene copolymer of chloromethylation in the formula, and RCl refers to the chlorine type resin anion(R.A) that contains glyoxaline structure, R
+OH
-Be the hydroxyl type anion resin that contains glyoxaline structure, DMF is N, dinethylformamide.
The preparation method of hydroxyl type anion resin who contains glyoxaline structure is following:
PS-DVB and DMF, g by weight: the ratio of volume mL is 1: 2 swelling, places and stirs 2h on the magnetic stirring apparatus; Add the N-Methylimidazole then, the mass ratio of N-Methylimidazole: PS-DVB is 2: 1-1: 2, and 72h refluxes in heat temperature raising to the 40 ℃ water-bath; After reaction finishes, with this resin filter, washing with alcohol; Drying gets RCl; Further the RCl resin is carried out anionresin with the methanol solution of NaOH, the 24h that in 40 ℃ of water-baths, refluxes, through methanol wash, drying obtains containing the hydroxyl type anion resin of glyoxaline structure; The methanol solution add-on of described NaOH is determined by following proportioning: the negatively charged ion Cl of RCl
-: the NaOH mol ratio is 1: 10-1: 30.
The hydroxyl type anion resin that contains glyoxaline structure is as biodiesel.This hydroxyl type anion resin that contains glyoxaline structure also can be used for other highly basic catalyzed reactions, like esterification, and Knoevenagel condensation, organic reactions such as Aldol condensation and Michael addition.
Contain the usage of the hydroxyl type anion resin of glyoxaline structure as the catalyzer of preparation biofuel, its step and condition are following:
Soya-bean oil and methyl alcohol are to add in the reactor drum in 1: 6～1: 20 according to mol ratio, add then contain glyoxaline structure the hydroxyl type anion exchange resin as catalyzer, the described hydroxyl type anion exchange resin that contains glyoxaline structure: the mass ratio of soya-bean oil is 0.5: 100～10: 100; Behind 40～60 ℃ of the heat temperature raisings; Constant temperature stirring and refluxing 8h, the reaction terminating after-filtration reclaims the hydroxyl type anion resin that contains glyoxaline structure, static layering; Separate two phases, obtain biofuel;
The described hydroxyl type anion resin catalyzer that contains glyoxaline structure, the recirculation of can regenerating is used.Described catalyst recirculation uses catalytic activity stable, and three times are used the transformation efficiency of artifact diesel oil is 90.33%, is the more satisfactory catalyzer of preparation biofuel.Five times are used the transformation efficiency of artifact diesel oil is 85.71%, and the productive rate of biofuel does not significantly descend.
The described hydroxyl type anion resin that contains glyoxaline structure is following as the step of the regenerated method of catalyzer in the preparation biofuel:
The hydroxyl type anion resin that will contain glyoxaline structure is used for catalyzed reaction accomplish after; Filter and take out this resin,, use methanol wash then with after the methanol wash it being immersed in 24h in the NaOH methanol solution; Drying obtains the hydroxyl type anion resin that regenerated contains glyoxaline structure; Described NaOH methanol solution consumption is: the basic sites and the mol ratio of NaOH that contain the hydroxyl type anion resin of glyoxaline structure are 1: 10-1: 30.
Beneficial effect: (1) hydroxyl type anion resin that contains glyoxaline structure provided by the invention is used for the preparation of biofuel as catalyzer.Described catalyzer has overcome ionic liquid and has reclaimed difficult problem, just can reclaim catalyzer through simple filtering.(2) the described catalyzer recirculation of can regenerating is used.It is stable to recycle catalytic activity, and it is 90% that the regeneration recirculation is used the transformation efficiency of artifact diesel oil three times, is the more satisfactory catalyzer of preparation biofuel.(3) described catalyzer usage in the preparation biofuel adopts conventional equipment, and temperature of reaction has only 40～60 ℃, mild condition, energy efficient.
Description of drawings
Fig. 1 PS-DVB, RCl, R
+OH
-The ir spectra spectrogram.
Fig. 2 PS-DVB and R
+OH
-Thermogravimetric curve.
Embodiment
Embodiment 1 contains the preparation of the hydroxyl type anion resin of glyoxaline structure
With 20g PS-DVB swelling in 40mL DMF, place and stir 2h on the magnetic stirring apparatus.Add 10g N-Methylimidazole then, the 72h that refluxes in heat temperature raising to the 40 ℃ water-bath, after reaction finishes, with this resin filter, washing with alcohol, drying gets RCl.Further the RCl resin is carried out anionresin with the methanol solution of NaOH, the 24h that in 40 ℃ of water-baths, refluxes, through methanol wash, drying is prepared R
+OH
-The methanol solution add-on of described NaOH is determined by following proportioning: the negatively charged ion Cl-of RCl: the NaOH mol ratio is 1: 10.
Can find out 1264cm in the ir spectra of PS-DVB from Fig. 1
-1Be-CH
2Among the Cl-CH
2-characteristic peak, at RCl and R
+OH
-Ir spectra in all do not have this characteristic peak.At RCl and R
+OH
-Infrared spectrogram in can find out corresponding 1572cm
-1And 1161cm
-1With 1573
-1And 1161
-Cm
1Vibration frequency is respectively the shock absorbing peak of C=C on the imidazole ring and the shock absorbing peak of C-N.Cl on this explanation PS-DVB is replaced by the N-Methylimidazole.Can find out PS-DVB and R from Fig. 2
+OH
-Decomposition temperature be respectively 251.02 ℃ and 223.61 ℃.R
+OH
-Due to 90 ℃ of minimizings that quality arranged are the water evaporation in the resin.Therefore, R
+OH
-Has good thermostability.Through the mensuration of ultimate analysis and specific surface, R
+OH
-In to contain the OH-basic sites be 3.12mmol/g, specific surface area is 131.18m
2/ g.
Embodiment 2
N-Methylimidazole consumption is 40g, and the methanol solution add-on of NaOH is: the negatively charged ion Cl of RCl
-: the NaOH mol ratio is 1: 20, and remaining is with embodiment 1.
Embodiment 3
N-Methylimidazole consumption is 20g, and the methanol solution add-on of NaOH is: the negatively charged ion Cl of RCl
-: the NaOH mol ratio is 1: 30, and remaining is with embodiment 1.
Embodiment 4 contains the hydroxyl type anion resin of glyoxaline structure as biodiesel
20g soya-bean oil and 8.61g methyl alcohol are added in the reactor drum, add R then
+OH
-As catalyzer, described R
+OH
-Add-on be 0.1g, behind 50 ℃ of the heat temperature raisings, constant temperature stirring and refluxing 8h.Obtain biofuel behind the reaction terminating, productive rate is 34.55%.
Embodiment 5 catalyzer R
+OH
-Consumption is 0.5g, and remaining is with embodiment 4.The productive rate of biofuel is 93.78%.
Embodiment 6 catalyzer R
+OH
-Consumption is 1.0g, 40 ℃ of heat temperature raisings, and remaining is with embodiment 4.The productive rate of biofuel is 80.82%.
Embodiment 7 catalyzer R
+OH
-Consumption is 1.5g, 60 ℃ of heat temperature raisings, and remaining is with embodiment 4.The productive rate of biofuel is 41.28%.
Embodiment 8 catalyzer R
+OH
-Consumption is 2.0g, and remaining is with embodiment 4.The productive rate of biofuel is 27.68%.
Embodiment 9 adds 20g soya-bean oil and 4.31g methyl alcohol in the reactor drum, adds catalyzer R
+OH
-0.5g behind 50 ℃ of the heat temperature raisings, constant temperature stirring and refluxing 8h obtains biofuel behind the reaction terminating.Productive rate is 23.35%.
Embodiment 10 adds methyl alcohol 6.46g, 40 ℃ of heat temperature raisings, and remaining is with embodiment 9.The productive rate of biofuel is 81.34%.
Embodiment 11 adds methyl alcohol 8.61g, and remaining is with embodiment 9.The productive rate of biofuel is 98.00%.
Embodiment 12 adds methyl alcohol 11.48g, 60 ℃ of heat temperature raisings, and remaining is with embodiment 9.The productive rate of biofuel is 98.05%.
Embodiment 13 adds methyl alcohol 14.35g, and remaining is with embodiment 9.The productive rate of biofuel is 98.75%.
14 1 kinds of regeneration that contain the hydroxyl type anion resin of glyoxaline structure of embodiment
With R
+OH
-After catalyzed reaction is accomplished, filter and take out resin, use methanol wash, it is immersed in 24h in the NaOH methanol solution, described NaOH methanol solution consumption is: R
+OH
-Basic sites and the mol ratio of NaOH be 1: 10, methanol wash, drying are used in the back.
Embodiment 15
Described NaOH methanol solution consumption is: R
+OH
-Basic sites and the mol ratio of NaOH be 1: 20, remaining is with embodiment 14.
Embodiment 16
Described NaOH methanol solution consumption is: R
+OH
-Basic sites and the mol ratio of NaOH be 1: 30, remaining is with embodiment 14.
Embodiment 17 contains the hydroxyl type anion resin catalyzer repeat performance of glyoxaline structure
20g soya-bean oil and 8.61g methyl alcohol are added in the reactor drum, add catalyzer R
+OH
-0.5g, behind 50 ℃ of the heat temperature raisings, constant temperature stirring and refluxing 8h.After reaction is accomplished, filter and take out resin, with this resin after embodiment 15 regeneration, reinforced once more repetition transesterification reaction, the result lists in table 1.After transesterification reaction was reused five times according to said process, the productive rate of biofuel did not significantly descend.
Table 1 catalyzer is reused the influence to its catalytic effect
| Cycle index | 1 | 2 | 3 | 4 | 5 |
| Transformation efficiency | 93.78％ | 92.03％ | 90.33％ | 89.50％ | 85.71％ |
Claims (3)
1. the method for making that contains the hydroxyl type anion resin of glyoxaline structure is characterized in that step and condition are following:
(1) the described hydroxyl type anion resin that contains glyoxaline structure, its structural formula is following:
(2) method for making of the described hydroxyl type anion resin that contains glyoxaline structure is following:
The styrene-divinylbenzene copolymer of chloromethylation, with N, dinethylformamide, g by weight: the ratio of volume mL is 1: 2 swelling; Place and stir 2h on the magnetic stirring apparatus, add the N-Methylimidazole then, the N-Methylimidazole: the mass ratio of the styrene-divinylbenzene copolymer of chloromethylation is 2: 1-1: 2; The 72h that refluxes in heat temperature raising to the 40 ℃ water-bath is after reaction finishes, with this resin filter; Washing with alcohol, drying must contain the chlorine type resin anion(R.A) of glyoxaline structure; The chlorine type resin anion(R.A) that further will contain glyoxaline structure carries out anionresin with the methanol solution of NaOH, the 24h that in 40 ℃ of water-baths, refluxes, and through methanol wash, drying obtains containing the hydroxyl type anion resin of glyoxaline structure; The methanol solution add-on of described NaOH is determined by following proportioning: the negatively charged ion Cl-that contains the chlorine type resin anion(R.A) of glyoxaline structure: the NaOH mol ratio is 1: 10-1: 30.
2. the application of the hydroxyl type anion resin that contains glyoxaline structure on the preparation biofuel of the said method for making preparation of claim 1 is characterized in that it is as the catalyzer of preparation biofuel.
3. the usage that contains the hydroxyl type anion resin of glyoxaline structure as the catalyzer of preparation biofuel as claimed in claim 2 is characterized in that its step and condition are following:
Soya-bean oil and methyl alcohol are to add in the reactor drum in 1: 6～1: 20 according to mol ratio, add then contain glyoxaline structure the hydroxyl type anion exchange resin as catalyzer, the described hydroxyl type anion exchange resin that contains glyoxaline structure: the mass ratio of soya-bean oil is 0.5: 100～10: 100; Behind 40～60 ℃ of the heat temperature raisings; Constant temperature stirring and refluxing 8h, the reaction terminating after-filtration reclaims the hydroxyl type anion resin that contains glyoxaline structure, static layering; Separate two phases, obtain biofuel;
The described hydroxyl type anion resin catalyzer that contains glyoxaline structure, the recirculation of can regenerating is used; Its regenerated method is following:
The hydroxyl type anion resin that will contain glyoxaline structure after being used for catalyzed reaction and accomplishing, filters and takes out this resin; With after the methanol wash it being immersed in 24h in the NaOH methanol solution; Use methanol wash then, drying obtains the hydroxyl type anion resin that regenerated contains glyoxaline structure; Described NaOH methanol solution consumption is: the basic sites and the mol ratio of NaOH that contain the hydroxyl type anion resin of glyoxaline structure are 1: 10-1: 30.
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| CN106391112A (en) * | 2015-08-03 | 2017-02-15 | 中国石油化工股份有限公司 | Immobilized ionic liquid catalyst and application thereof |
| CN106391115A (en) * | 2015-08-03 | 2017-02-15 | 中国石油化工股份有限公司 | Immobilized ionic liquid catalyst and application thereof |
| CN105566517B (en) * | 2015-12-28 | 2018-10-12 | 中南大学 | A kind of preparation method and applications of nitrogen heterocyclic functionalization ion exchange material |
| CN108586963A (en) * | 2018-04-28 | 2018-09-28 | 台州学院 | A kind of application of ionic liquid block polymer in supercritical carbon dioxide microporous foam |
| CN115212858B (en) * | 2022-08-31 | 2024-04-12 | 燕山大学 | Immobilized heteropolyacid ionic liquid composite material for purifying heavy metals in water body and preparation method and application thereof |
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Effective date of registration: 20131018 Address after: Changzhou City, Jiangsu province Hehai road 213000 No. 9 Patentee after: Changzhou Institute of Energy Storage Materials & Devices Address before: 130022 Changchun people's street, Jilin, No. 5625 Patentee before: Changchun Institue of Applied Chemistry, Chinese Academy of Sciences |