CN109777625A - The synthetic method of biodiesel - Google Patents
The synthetic method of biodiesel Download PDFInfo
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- CN109777625A CN109777625A CN201711111506.XA CN201711111506A CN109777625A CN 109777625 A CN109777625 A CN 109777625A CN 201711111506 A CN201711111506 A CN 201711111506A CN 109777625 A CN109777625 A CN 109777625A
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Abstract
The step of the present invention relates to a kind of synthetic methods of biodiesel, are included under the conditions of ester exchange reaction, and grease and short chain alcohol and ion-exchange resin catalyst contact；The ion-exchange resin catalyst has following structure general formula:Wherein,For macroporous type nanocomposite resin matrix；M‑For anion, it is selected from phosphotungstic acid root, phosphomolybdic acid root, silico-tungstic acid root, silicomolybdic acid root, arsenowolframic acid root, arsenic molybdate, germanotungstic acid root, germanium molybdate, tungstovanadophosphoric acid root or molybdovanaphosphoric acid root；POSS is cage-type silsesquioxane unit；
Description
Technical field
The present invention relates to a kind of synthetic methods of biodiesel.
Background technique
With the continuous consumption of traditional fossil energy, people are for researching and developing environmentally protective, renewable new energy demand day
It is beneficial urgent.Conventional fossil fuel can generate sulfur dioxide, nitrogen oxides and other a large amount of dust in combustion, to ecology
Environment causes great damage.And biodiesel is as a kind of green energy resource, compared with petrifaction diesel, have it is renewable, can biology
Degradation, waste discharge is low, Cetane number is high, flash-point is high, using it is safe the features such as.
The preparation method of biodiesel, which mainly has, directly to be used method, is used in mixed way method, microemulsion method, high-temperature cracking method and ester
Exchange process.At present industrially using it is more be ester-interchange method, it be with oil crops such as soybean, rape, cotton, palm etc., it is wild
The water plants such as oil generation tannin plant and engineering microalgae grease and animal fat, food garbage oil etc. are feedstock oil, with short chain alcohol
Fatty acid methyl Ester is made by transesterification or thermochemical processes, to replace petrifaction diesel.
Method used by preparing biodiesel by ester interchange is more, such as homogeneous acid-base method, Lipids Enzymatic, supercritical methanol technology and
Heterogeneous acid-base method etc..Traditional homogeneous acid-base catalysis method post-processes cumbersome, a large amount of three wastes of generation etc. there are equipment burn into and asks
Topic；Enzyme catalyst is since its is environmental-friendly by numerous concerns in Lipids Enzymatic, but the reaction time needed for enzymatic is longer, is easy
Inactivation, while its usage amount is larger, limits the extensive use of enzyme catalyst；Preparation of Biodiesel by Supercritical Method high conversion rate,
But high-temperature and high-pressure conditions are needed, equipment requirement is high and energy consumption is high；Although heterogeneous acid-base catalysis method catalyst recycling is convenient, also deposit
It is low in reactivity, there is certain limitation.Therefore environmental-friendly effective catalyst is developed as current research hotspot.
Acidic ion liquid is provided simultaneously with traditional liquid as a kind of novel environmentally friendly solvent and effective catalyst
The high density reaction active site of acid catalyst and the fixedness of solid acid, and because its molecular structure and acidity have and can design
Property, it is considered to be one of most promising green catalyst.But acidic ion liquid there is also viscosity big, at high cost, product/urge
Agent separation is inconvenient, makes it in the process of industrialization of catalysis biological diesel oil by biggish limitation.
Document CN201410442179.6 discloses a kind of preparation side of N- Methyl-N-alkyl film type ionic liquid
Method, catalyst of the ionic liquid as bio-oil and methanol preparing biodiesel by ester exchange, activity is high, and dosage is few, performance
Also more stable.It is 40 in methanol/soybean oil alcohol oil rate, temperature is 60 degree reaction 1 hour lower, and the yield of biodiesel is reachable
93.7%.
It is excellent that immobilized ionic liquid combines high activity and the easily separated, recycling of heterogeneous catalysis of homogeneous catalyst etc.
Point is a kind of novel green catalyst, has huge application potential in biodiesel synthesis field.
Document CN201510064336.9 discloses a kind of acidic ion liquid of biodiesel synthesis cultivation property catalyst admittedly,
The patent is solid by ionic liquid [2-MPYR-BS] [HSO4], [HMIM-BS] [HSO4] or [PYR-BS] [HSO4] using infusion process
It plants to introducing on the mesopore molecular sieve Al-MCM-41 of Al, solid cultivationization ionic-liquid catalyst is prepared, be used for transesterification legal system
Standby biodiesel.Using Al-MCM-41- [2-MPYR-BS] [HSO4] as catalyst, under certain alcohol oil rate, reacted at 150 DEG C
6 hours, the yield of biodiesel was up to 97.0%.Biodiesel is environmentally friendly without neutralizing washing, and catalyst is with excellent
Different catalytic activity, Yi Huishou.But by the type of cultivation admittedly ionic-liquid catalyst prepared by infusion process, there are still certain activity
Center losing issue, after which uses 5 times, the yield of biodiesel has fallen to 91.5%, and repeat performance is poor.
Document CN201710337145.4 discloses a kind of preparation method of biodiesel special solid base catalyst, utilizes
Polymer emulsion adsorbs saleratus, calcines through two steps, forms spongy porosu solid base catalyst, carrier is equal with effective component
For porous structure, although solving the easy blockage problem in catalyst duct made from traditional infusion process.But the repetition of the catalyst
Service performance is poor, and after 5 times are reused, the yield of biodiesel is reduced to 88.9% via 94.6%.
The catalytic activity of solid-carrying type ionic-liquid catalyst depends not only on the performance of ionic liquid itself, additionally depends on load
The various performances of body, such as heat resistance, solvent resistance, porosity etc..It can be seen that designing a kind of with high activity, repetition
The excellent biodiesel preparation of utility is of crucial importance with ester exchange catalyst.
Summary of the invention
The present invention provides a kind of synthetic method of biodiesel.The method includes under the conditions of ester exchange reaction, grease
The step of being contacted with short chain alcohol and ion-exchange resin catalyst；The ion-exchange resin catalyst has following structure logical
Formula:
Wherein,For macroporous type nanocomposite resin matrix；
M-For anion, selected from phosphotungstic acid root, phosphomolybdic acid root, silico-tungstic acid root, silicomolybdic acid root, arsenowolframic acid root, arsenic molybdate,
Germanotungstic acid root, germanium molybdate, tungstovanadophosphoric acid root or molybdovanaphosphoric acid root；
POSS is cage-type silsesquioxane unit, and general formula is (- SiO1.5)m；M is 6,8,10 or 12；
For glyoxaline cation unit；
Linking group of the R between POSS unit and glyoxaline cation unit, R are alkylidene or arylene；
The macroporous type nanocomposite resin matrix is styrene monomer, comonomer, nano material and pore-foaming agent warp
The nanometer macroporous type copolymer that in-situ copolymerization obtains；The nano material is selected from multi-walled carbon nanotube, single-walled carbon nanotube, C60
Or at least one of C70 fullerene.
According to an aspect of the present invention, content of the POSS unit in the ion exchange resin is 2~8 weight %.
According to an aspect of the present invention, M-For phosphotungstic acid radical ion.
According to an aspect of the present invention, alkylidene is selected from methylene, ethylidene or propylidene；Arylene is selected from sub- benzene
Base, naphthylene or sub- benzyl.
According to an aspect of the present invention, the styrene monomer is selected from styrene, α-methylstyrene or 4- butyl
At least one of styrene, optimization styrene.
According to an aspect of the present invention, the comonomer be selected from ethyleneglycol dimethyacrylate, diallyl benzene,
At least one of divinyl phenylmethane or divinylbenzene, preferably divinylbenzene.
According to an aspect of the present invention, the pore-foaming agent is selected from aliphatic hydrocarbon, polystyrene, gasoline, poly- (propylene glycol), gathers
At least one of (ethylene glycol), dimethyl silicone polymer, fatty acid or paraffin, preferably polystyrene.
According to an aspect of the present invention, the dosage of styrene monomer is 85~95 parts, the dosage of comonomer is 2~
5 parts, the dosage of nano material is 0.1~3 part, and the dosage of pore-foaming agent is 10~100 parts.
According to an aspect of the present invention, the preferred multi-walled carbon nanotube of the nano material.
According to an aspect of the present invention, the grease is selected from any one of the vegetable and animals oils of fatty glyceride.
Such as the vegetable oil such as soybean oil, rapeseed oil, cottonseed oil or palm oil, the water plants grease such as wild plant oil plant, engineering microalgae,
And animal fat, food garbage oil etc..
According to an aspect of the present invention, the short chain alcohol is any in methanol, ethyl alcohol, propyl alcohol or butanol.
According to an aspect of the present invention, it is (10 that the ester exchange reaction condition, which includes: the molar ratio of short chain alcohol and grease,
~50): 1, catalyst amount is the 1~15% of raw oil material quality, and 40~180 DEG C of reaction temperature, the reaction time 1~24 is small
When.
The preparation method of heretofore described ion-exchange resin catalyst, comprising the following steps:
A) auxiliary agent is made into the water solution A that weight percent concentration is 0.5~2%, styrene monomer, copolymerization is single
Body, nano material, initiator and pore-foaming agent wiring solution-forming B；Wherein, the styrene monomer is selected from styrene, Alpha-Methyl benzene
At least one of ethylene or 4- butylstyrene；The comonomer is selected from ethyleneglycol dimethyacrylate, diallyl
At least one of benzene, divinyl phenylmethane or divinylbenzene；The nano material is selected from multi-walled carbon nanotube, single wall
At least one of carbon nanotube, C60 or C70 fullerene；The initiator be selected from benzoyl peroxide, azodiisobutyronitrile,
At least one of lauroyl peroxide or isopropyl benzene hydroperoxide；The pore-foaming agent be selected from aliphatic hydrocarbon, polystyrene, gasoline,
At least one of poly- (propylene glycol), poly(ethylene glycol), dimethyl silicone polymer, fatty acid or paraffin；The auxiliary agent is selected from poly-
At least one of vinyl alcohol, gelatin, starch, methylcellulose, bentonite or calcium carbonate；Based on parts by weight, styrene list
The dosage of body is 85~95 parts, and the dosage of comonomer is 2~5 parts, and the dosage of nano material is 0.1~3 part, the use of initiator
Amount is 0.1~10 part；The dosage of pore-foaming agent is 10~100 parts；The dosage of auxiliary agent is the 150~400% of monomer dosage；
B) by solution B 60~75 DEG C prepolymerization 0.5~2.5 hour, solution B is mixed with solution A then, is warming up to 70
~90 DEG C are reacted 5~15 hours, then are warming up to 90~100 DEG C and are reacted 5~15 hours；After reaction, through extracting, washing, mistake
Filter, dry, sieving, obtain 0.35~0.60 millimeter of particle size range of compound macroporous microsphere；
C) make the compound macroporous microsphere chloromethylation: being added in compound macroporous microsphere and be equivalent to compound macroporous microsphere weight
The chloromethylation reagents of amount 200~500%, and it is equivalent to the zinc chloride catalyst of compound macroporous microsphere weight 20~70%,
It is reacted 8~30 hours at 30~60 DEG C, is filtered, washed to obtain compound macropore chlorine ball；The chloromethylation reagents are selected from chlorine
At least one of methyl ether, dichloroethyl ether or Isosorbide-5-Nitrae-dichloro methyl butyl ether；
D) it by the compound macropore chlorine ball, the mixture of imidazoles and acetonitrile, is reacted at 60~90 DEG C, obtains compound imidazoles
Microballoon；In the mixture, the molar ratio of compound macropore chlorine ball, imidazoles and acetonitrile is 1:(1~2): (30~150)；
E) by the POSS compound of the compound imidazoles microballoon and halogenated alkyl according to imidazole functionalities and halogenated functional group
Equimolar mixing, is dissolved in tetrahydrofuran, 24~72 hours at 100 DEG C, filters after reaction, and washing obtains compound miaow
Azoles/POSS microballoon；The POSS compound of the halogenated alkyl is selected from eight chloromethyl POSS, eight chloroethyl POSS, eight chloropropyls
At least one of POSS；
F) the compound imidazoles/POSS microballoon brine, wherein compound imidazoles/POSS microballoon and salting liquid rub
You are than being (1:1)~(1:10)；The concentration of salting liquid is 0.1~1mol/L；It is washed with deionized after washing to pH=
7, obtain the ion exchange resin.The salting liquid is selected from phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid, silicomolybdic acid, arsenowolframic acid, arsenic molybdenum
At least one of acid, germanotungstic acid, germanium molybdic acid, tungstovanadophosphoric acid, molybdovanaphosphoric acid salting liquid.
Beneficial effects of the present invention: the ion-exchange resin catalyst in the present invention contains two different nano materials: receiving
Rice carbon material and cage-type silsesquioxane (Polyhedral oligomeric silsesquioxanes, abbreviation POSS).Nanometer
Carbon material and monomer, comonomer are introduced into resin matrix by in-situ polymerization under initiator effect, improve resin base
The glass transition temperature of body；Simultaneously because the introducing of nano-carbon material, increases the resistance to swelling energy of resin matrix.And POSS
Comprising the inorganic supporting structure being made of Si and O, the good heat resistance of ion exchange resin is imparted, thermal stability significantly mentions
It is high.The preferred solution of the invention is the macroporous type in situ copolymerization of the styrene, divinylbenzene and multi-walled carbon nanotube of chloromethylation
Resin matrix is reacted with imidazoles, obtains compound imidazoles microballoon, then passes through the POSS compound of imidazole group and halogenated alkyl
Reaction finally carries out ion-exchange reactions with salting liquid again, and the macroporous type ion containing two kinds of different nano materials is prepared and hands over
Change resin.It is reacted by the in-situ copolymerization between carbon nanotube and monomer, comonomer and realizes carbon nanotube and polymeric matrix
Covalent bond, and by the chemical reaction of halogenated alkyl POSS compound and imidazole group realize POSS and resin matrix it
Between combination.
The macroreticular ion exchange resin catalyst containing two kinds of different nano materials in the present invention is for grease and short chain
The ester exchange reaction of alcohol, has the advantage that
(1) catalyst prepared by is used for preparing biodiesel by ester interchange, and catalytic activity is high；
(2) catalyst easily recycles, and stability is good, reusable.
The present invention will be further described below by way of examples, it should be noted however that protection model of the invention
It encloses not that this is limited by this, but is determined by the appended claims.
It should be strongly noted that two or more aspects (or embodiment) disclosed in the context of the present specification
Any combination, the technical solution formed therefrom it can belong to a part of this specification original disclosure each other, while
It falls under the scope of the present invention.
Specific embodiment
The preparation of [embodiment 1] ion-exchange resin catalyst
47.0 grams of styrene, 2.3 grams of divinylbenzenes, 30 grams of polystyrene and 1.6 are added in 500 milliliters of three-necked flasks
Gram benzoyl peroxide initiator, is stirred to react 1.5 hours at 60 DEG C；Then 0.6 gram of multi-walled carbon nanotube is added, continues to stir
Mix progress prepolymerization in 1 hour.The 260 ml deionized water solution for being dissolved with 2.0 grams of gelatin are added.Mixing speed is adjusted, together
When be gradually warming up to 80 DEG C, react 5 hours；It is warming up to 90 DEG C again, reacts 5 hours, is finally warming up to 98 DEG C, reacts 8 hours.Instead
After answering, supernatant liquid is poured out, is washed with 85 DEG C of hot water, then washed with cold water, is then filtered, is put into 80 DEG C of bakings in baking oven
It is dry, sieving, compound macroporous microsphere A1 of the collection cut size within the scope of 0.35~0.60mm.
Compound macroporous microsphere chloromethylation: in the three-necked flask of 500ml, be added 40 grams of compound macroporous microsphere A1 and
200ml chloromethyl ether is stored at room temperature 3 hours, starts to stir, and it is catalyst that 15 grams of zinc chloride, which are added, and it is small to be warming up to 50 DEG C of reactions 12
When, it is cooled to room temperature after chloromethylation, filters out chlorination mother solution, washed repeatedly with methanol, dry 8 hours, obtain at 100 DEG C
To compound macropore chlorine ball A1.
30 grams of compound macropore chlorine ball A1 (chlorinity is 2.84mmol Cl/g), imidazoles are added in 500ml there-necked flask
(84.0mmol) and 200ml acetonitrile, reacts 24 hours at 80 DEG C, are cooled to room temperature, and filter, successively use ethyl acetate,
The HCl of 0.1mol/L, deionized water, methanol washing, then 60 DEG C of vacuum bakings obtain compound imidazoles microballoon A1 in 12 hours.
In 500ml three-necked flask, the compound imidazoles microballoon A2 of 30 grams of addition (imidazole group content is 2.6mmol/g), 7.9
Gram eight chloromethyl silsesquioxanes and 300ml tetrahydrofuran filter after reaction 24 hours at 100 DEG C, with tetrahydro furan
Mutter, deionized water is successively washed, obtain compound imidazoles/POSS microballoon A1.
In 1000ml three-necked flask, it is 0.1mol/L's that 30 grams of compound imidazoles/POSS microballoon A1,500ml concentration, which is added,
Progress ion-exchange reactions 24 hours is stirred at room temperature in the deionized water solution of sodium phosphotungstate；It is then washed with deionized straight
To washing lotion pH=7, the ion-exchange resin catalyst of the different nano materials of of the invention two kinds is obtained after vacuum drying, is denoted as
Cat-A1, wherein POSS unit content is 3.9%, and structural formula is as follows:
The preparation of [embodiment 2] ion-exchange resin catalyst
In 500 milliliters of three-necked flasks be added containing initiator monomer mixture solution (60.0 grams of styrene, 1.0 grams
Divinylbenzene, 60 grams of polystyrene, 1.6 grams of multi-walled carbon nanotubes and 1.0 grams of benzoyl peroxides, the solution are stirred prior to 70 DEG C
Mix reaction 0.5 hour), blender is started, the mixed solution of 200 ml deionized waters and 4 grams of polyvinyl alcohol is added, is warming up to 85
DEG C, it reacts 3 hours, then be warming up to 90 DEG C, reacts 9 hours, be finally warming up to 100 DEG C, react 10 hours.After reaction, incline
Supernatant liquid is poured out, is washed with 85 DEG C of hot water, then washed with cold water, is then filtered, 80 DEG C of drying in baking oven is put into, is sieved, receive
Collect compound macroporous microsphere B1 of the partial size within the scope of 0.35~0.60 millimeter.
The chloromethylation of complex microsphere: in 500 milliliters of three-necked flask, 50 grams of complex microsphere B1 and 200 milliliters are added
Dichloroethyl ether is stored at room temperature 6 hours, and it is catalyst that 30 grams of zinc chloride, which are added, starts to stir, and is warming up to 50 DEG C and is reacted 24 hours, chlorine
It is cooled to room temperature after methylation, filters out chlorination mother solution, washed repeatedly with methanol, dried 8 hours, answered at 100 DEG C
Close macropore chlorine ball B1.
50 grams of compound macropore chlorine ball B (chlorinity is 4.1mmol Cl/g), imidazoles are added in 500ml there-necked flask
(205.0mmol) and 300ml acetonitrile, reacts 16 hours at 80 DEG C, are cooled to room temperature, and filter, successively use ethyl acetate,
The HCl of 0.1mol/L, deionized water, methanol washing, then 60 DEG C of vacuum bakings obtain compound imidazoles microballoon B1 in 12 hours.
In 1000ml three-necked flask, 50 grams of compound imidazoles microballoon B1 (imidazole group content is 3.6mmol/g) are added,
18.3 gram of eight chloromethyl silsesquioxane and 500ml tetrahydrofuran filter after reaction 72 hours at 100 DEG C, with four
Hydrogen furans, deionized water are successively washed, and compound imidazoles/POSS microballoon B1 is obtained.
In 1000ml three-necked flask, it is 1.0mol/L's that 40 grams of compound imidazoles/POSS microballoon B1,400ml concentration, which is added,
Progress ion-exchange reactions 12 hours is stirred at room temperature in the deionized water solution of sodium phosphotungstate；It is then washed with deionized straight
To washing lotion pH=7, the ion-exchange resin catalyst of the different nano materials of of the invention two kinds is obtained after vacuum drying, is denoted as
Cat-B1, wherein POSS unit content is 4.2%, and structural formula is as follows:
The preparation of [embodiment 3] ion-exchange resin catalyst
In 500 milliliters of three-necked flasks be added containing initiator monomer mixture solution (42.5 grams of styrene, 2.5 grams
Divinylbenzene, 10 grams of polystyrene, 0.1 gram of multi-walled carbon nanotube and 2.0 grams of benzoyl peroxides, the solution are stirred prior to 70 DEG C
Mix reaction 1.5 hours), the mixed solution of 200 ml deionized waters and 4 grams of polyvinyl alcohol is added, is warming up to 85 DEG C, reaction 3 is small
When, then 90 DEG C are warming up to, it reacts 9 hours, is finally warming up to 100 DEG C, react 10 hours.After reaction, upper liquid is poured out
Body is washed with 85 DEG C of hot water, then is washed with cold water, is then filtered, and 80 DEG C of drying in baking oven, sieving are put into, and collection cut size exists
Compound macroporous microsphere C1 within the scope of 0.35~0.60 millimeter.
The chloromethylation of complex microsphere: in 250 milliliters of three-necked flask, 20 grams of complex microsphere C1 and 100 milliliters are added
Isosorbide-5-Nitrae-dichloro methyl butyl ether is stored at room temperature 6 hours, and it is catalyst that 8 grams of zinc chloride, which are added, starts to stir, and is warming up to 30 DEG C instead
It answers 10 hours, is cooled to room temperature after chloromethylation, filters out chlorination mother solution, washed repeatedly with methanol, dry 8 at 100 DEG C
Hour, obtain compound macropore chlorine ball C1.
20 grams of compound macropore chlorine ball C1 (chlorinity is 1.4mmol Cl/g), imidazoles are added in 250ml there-necked flask
(28.0mmol) and 150ml acetonitrile, reacts 16 hours at 90 DEG C, are cooled to room temperature, and filter, successively use ethyl acetate,
The HCl of 0.1mol/L, deionized water, methanol washing, then 60 DEG C of vacuum bakings obtain compound imidazoles microballoon C1 in 12 hours.
In 250ml three-necked flask, the compound imidazoles microballoon C1 of 20 grams of addition (imidazole group content is 1.3mmol/g), 3.0
Gram eight chloroethyl silsesquioxanes and 150ml tetrahydrofuran filter after reaction 72 hours at 100 DEG C, with tetrahydro furan
Mutter, deionized water is successively washed, obtain compound imidazoles/POSS microballoon C1.
In 500ml three-necked flask, the phosphorus that 20 grams of compound imidazoles/POSS microballoon C1,300ml concentration is 0.5mol/L is added
Progress ion-exchange reactions 12 hours is stirred at room temperature in the deionized water solution of sodium tungstate；Then be washed with deionized until
Washing lotion pH=7 obtains the ion-exchange resin catalyst of the different nano materials of of the invention two kinds, is denoted as Cat- after vacuum drying
C1, wherein POSS unit content is 3.0%, and structural formula is as follows:
The preparation of [embodiment 4] ion-exchange resin catalyst
47.0 grams of styrene, 2.3 grams of divinylbenzenes, 40 grams of polystyrene and 1.6 are added in 500 milliliters of three-necked flasks
Gram benzoyl peroxide initiator, is stirred to react 2.0 hours at 60 DEG C；Then 0.6 gram of single-layer graphene is added, continues to stir
Progress prepolymerization in 1 hour.The 260 ml deionized water solution for being dissolved with 2.0 grams of gelatin are added.Mixing speed is adjusted, simultaneously
80 DEG C are gradually warming up to, is reacted 5 hours；It is warming up to 90 DEG C again, reacts 5 hours, is finally warming up to 98 DEG C, reacts 6 hours.Reaction
After, supernatant liquid is poured out, is washed with 85 DEG C of hot water, then washed with cold water, is then filtered, is put into 80 DEG C of bakings in baking oven
It is dry, sieving, compound macroporous microsphere A2 of the collection cut size within the scope of 0.35~0.60mm.
Compound macroporous microsphere chloromethylation: in the three-necked flask of 500ml, be added 40 grams of compound macroporous microsphere A2 and
200ml chloromethyl ether is stored at room temperature 3 hours, starts to stir, and it is catalyst that 20 grams of zinc chloride, which are added, and it is small to be warming up to 60 DEG C of reactions 10
When, it is cooled to room temperature after chloromethylation, filters out chlorination mother solution, washed repeatedly with methanol, dry 8 hours, obtain at 100 DEG C
To compound macropore chlorine ball A2.
30 grams of compound macropore chlorine ball A2 (chlorinity is 3.34mmol Cl/g), imidazoles are added in 500ml there-necked flask
(992.0mmol) and 200ml acetonitrile, reacts 24 hours at 70 DEG C, are cooled to room temperature, and filter, successively use ethyl acetate,
The HCl of 0.1mol/L, deionized water, methanol washing, then 60 DEG C of vacuum bakings obtain compound imidazoles microballoon A2 in 12 hours.
In 500ml three-necked flask, the compound imidazoles microballoon A2 of 30 grams of addition (imidazole group content is 3.0mmol/g), 9.1
Gram eight chloromethyl silsesquioxanes and 300ml tetrahydrofuran filter after reaction 24 hours at 100 DEG C, with tetrahydro furan
Mutter, deionized water is successively washed, obtain compound imidazoles/POSS microballoon A2.
In 1000ml three-necked flask, it is 0.1mol/L's that 30 grams of compound imidazoles/POSS microballoon A2,500ml concentration, which is added,
Progress ion-exchange reactions 24 hours is stirred at room temperature in the deionized water solution of sodium phosphotungstate；It is then washed with deionized straight
To washing lotion pH=7, the ion-exchange resin catalyst of the different nano materials of of the invention two kinds is obtained after vacuum drying, is denoted as
Cat-A2, wherein POSS unit content is 4.0%, and structural formula is as follows:
The preparation of [embodiment 5] ion-exchange resin catalyst
In 500 milliliters of three-necked flasks be added containing initiator monomer mixture solution (60.0 grams of styrene, 1.0 grams
Divinylbenzene, 60 grams of polystyrene, 1.6 grams of single-layer graphenes and 1.0 grams of benzoyl peroxides, the solution are stirred prior to 70 DEG C
Reaction 0.5 hour), blender is started, the mixed solution of 200 ml deionized waters and 4 grams of polyvinyl alcohol is added, is warming up to 85
DEG C, it reacts 3 hours, then be warming up to 90 DEG C, reacts 9 hours, be finally warming up to 100 DEG C, react 10 hours.After reaction, incline
Supernatant liquid is poured out, is washed with 85 DEG C of hot water, then washed with cold water, is then filtered, 80 DEG C of drying in baking oven is put into, is sieved, receive
Collect compound macroporous microsphere B2 of the partial size within the scope of 0.35~0.60 millimeter.
The chloromethylation of complex microsphere: in 500 milliliters of three-necked flask, 50 grams of complex microsphere B2 and 200 milliliters are added
Dichloroethyl ether is stored at room temperature 6 hours, and it is catalyst that 30 grams of zinc chloride, which are added, starts to stir, and is warming up to 50 DEG C and is reacted 30 hours, chlorine
It is cooled to room temperature after methylation, filters out chlorination mother solution, washed repeatedly with methanol, dried 8 hours, answered at 100 DEG C
Close macropore chlorine ball B2.
50 grams of compound macropore chlorine ball B2 (chlorinity is 4.2mmol Cl/g), imidazoles are added in 500ml there-necked flask
(210.0mmol) and 300ml acetonitrile, reacts 16 hours at 80 DEG C, are cooled to room temperature, and filter, successively use ethyl acetate,
The HCl of 0.1mol/L, deionized water, methanol washing, then 60 DEG C of vacuum bakings obtain compound imidazoles microballoon B2 in 12 hours.
In 1000ml three-necked flask, 50 grams of compound imidazoles microballoon B2 (imidazole group content is 3.7mmol/g) are added,
18.8 gram of eight chloromethyl silsesquioxane and 500ml tetrahydrofuran filter after reaction 72 hours at 100 DEG C, with four
Hydrogen furans, deionized water are successively washed, and compound imidazoles/POSS microballoon B2 is obtained.
In 1000ml three-necked flask, it is 1.0mol/L's that 40 grams of compound imidazoles/POSS microballoon B2,400ml concentration, which is added,
Progress ion-exchange reactions 12 hours is stirred at room temperature in the deionized water solution of sodium phosphotungstate；It is then washed with deionized straight
To washing lotion pH=7, the ion-exchange resin catalyst of the different nano materials of of the invention two kinds is obtained after vacuum drying, is denoted as
Cat-B2, wherein POSS unit content is 4.2%, and structural formula is as follows:
The preparation of [embodiment 6] ion-exchange resin catalyst
In 500 milliliters of three-necked flasks be added containing initiator monomer mixture solution (42.5 grams of styrene, 2.5 grams
Divinylbenzene, 10 grams of polystyrene, 0.1 gram of single-layer graphene and 2.0 grams of benzoyl peroxides, the solution are stirred prior to 70 DEG C
Reaction 1.5 hours), the mixed solution of 200 ml deionized waters and 4 grams of polyvinyl alcohol is added, is warming up to 85 DEG C, reacts 3 hours,
It is warming up to 90 DEG C again, reacts 9 hours, is finally warming up to 100 DEG C, reacts 10 hours.After reaction, supernatant liquid is poured out,
Washed with 85 DEG C of hot water, then washed with cold water, then filtered, be put into baking oven 80 DEG C of drying, sieving, collection cut size 0.35~
Compound macroporous microsphere C2 within the scope of 0.60 millimeter.
The chloromethylation of complex microsphere: in 250 milliliters of three-necked flask, 20 grams of complex microsphere C2 and 100 milliliters are added
Isosorbide-5-Nitrae-dichloro methyl butyl ether is stored at room temperature 6 hours, and it is catalyst that 8 grams of zinc chloride, which are added, starts to stir, and is warming up to 30 DEG C instead
It answers 12 hours, is cooled to room temperature after chloromethylation, filters out chlorination mother solution, washed repeatedly with methanol, dry 8 at 100 DEG C
Hour, obtain compound macropore chlorine ball C2.
20 grams of compound macropore chlorine ball C2 (chlorinity is 1.6mmol Cl/g), imidazoles are added in 250ml there-necked flask
(32.0mmol) and 150ml acetonitrile, reacts 16 hours at 90 DEG C, are cooled to room temperature, and filter, successively use ethyl acetate,
The HCl of 0.1mol/L, deionized water, methanol washing, then 60 DEG C of vacuum bakings obtain compound imidazoles microballoon C2 in 12 hours.
In 250ml three-necked flask, the compound imidazoles microballoon C2 of 20 grams of addition (imidazole group content is 1.5mmol/g), 3.6
Gram eight chloroethyl silsesquioxanes and 150ml tetrahydrofuran filter after reaction 72 hours at 100 DEG C, with tetrahydro furan
Mutter, deionized water is successively washed, obtain compound imidazoles/POSS microballoon C2.
In 500ml three-necked flask, the phosphorus that 20 grams of compound imidazoles/POSS microballoon C2,300ml concentration is 0.5mol/L is added
Progress ion-exchange reactions 12 hours is stirred at room temperature in the deionized water solution of sodium tungstate；Then be washed with deionized until
Washing lotion pH=7 obtains the ion-exchange resin catalyst of the different nano materials of of the invention two kinds, is denoted as Cat- after vacuum drying
C2, wherein POSS unit content is 3.2%, and structural formula is as follows:
The preparation of [comparative example 1] comparative catalyst
Nano material is not added prepares macroporous microsphere: 47.0 grams of styrene of addition in 500 milliliters of three-necked flasks, 2.3 grams
260 millis for being dissolved with 2.0 grams of gelatin are added in divinylbenzene, 30 grams of polystyrene and 1.6 grams of benzoyl peroxide initiators
Rise deionized water solution.Mixing speed is adjusted, is stirred 2 hours.It is stirred to react at 60 DEG C 2.0 hours, is then gradually warming up to
It 80 DEG C, reacts 5 hours；It is warming up to 90 DEG C again, reacts 5 hours, is finally warming up to 98 DEG C, reacts 8 hours.After reaction, incline
Supernatant liquid is poured out, is washed with 85 DEG C of hot water, then washed with cold water, is then filtered, 80 DEG C of drying in baking oven is put into, is sieved, receive
Collect macroporous microsphere DZ-1 of the partial size within the scope of 0.35~0.60mm.
Macroporous microsphere chloromethylation: in the three-necked flask of 500ml, 40 grams of macroporous microsphere DZ-1 and 200ml chloromethanes are added
Ether is stored at room temperature 3 hours, starts to stir, and it is catalyst that 15 grams of zinc chloride, which are added, is warming up to 50 DEG C and reacts 12 hours, chloromethyl
It is cooled to room temperature after change, filters out chlorination mother solution, washed repeatedly with methanol, dried 8 hours at 100 DEG C, obtain macropore chlorine
Ball DZ-1.
Halogenated alkyl POSS compound is not used: 30 grams of macropore chlorine ball DZ-1 (chlorinities being added in 500ml there-necked flask
For 2.9mmol Cl/g), N- methylimidazole (87.0mmol) and 200ml acetonitrile, is reacted 24 hours at 80 DEG C, be cooled to room
Temperature, filtering, is successively washed with ethyl acetate, the HCl of 0.1mol/L, deionized water, methanol, is then dried 12 hours for 60 DEG C of vacuum
To imidazoles microballoon DZ-1.
In 1000ml three-necked flask, the sodium phosphotungstate that 30 grams of imidazoles microballoon DZ-1,500ml concentration are 0.1mol/L is added
Deionized water solution be stirred at room temperature progress ion-exchange reactions 24 hours；It is then washed with deionized until washing lotion pH
=7, ion-exchange resin catalyst is obtained after vacuum drying, is denoted as Cat-DZ-1, structural formula is as follows:
The preparation of [comparative example 2] comparative catalyst
47.0 grams of styrene, 2.3 grams of divinylbenzenes, 30 grams of polystyrene and 1.6 are added in 500 milliliters of three-necked flasks
Gram benzoyl peroxide initiator, is stirred to react 1.5 hours at 60 DEG C；Then 0.6 gram of multi-walled carbon nanotube is added, continues to stir
Mix progress prepolymerization in 1 hour.The 260 ml deionized water solution for being dissolved with 2.0 grams of gelatin are added.Mixing speed is adjusted, together
When be gradually warming up to 80 DEG C, react 5 hours；It is warming up to 90 DEG C again, reacts 5 hours, is finally warming up to 98 DEG C, reacts 8 hours.Instead
After answering, supernatant liquid is poured out, is washed with 85 DEG C of hot water, then washed with cold water, is then filtered, is put into 80 DEG C of bakings in baking oven
It is dry, sieving, compound macroporous microsphere DZ-2 of the collection cut size within the scope of 0.35~0.60mm.
Compound macroporous microsphere chloromethylation: in the three-necked flask of 500ml, be added 40 grams of compound macroporous microsphere DZ-2 and
200ml chloromethyl ether is stored at room temperature 3 hours, starts to stir, and it is catalyst that 15 grams of zinc chloride, which are added, and it is small to be warming up to 50 DEG C of reactions 12
When, it is cooled to room temperature after chloromethylation, filters out chlorination mother solution, washed repeatedly with methanol, dry 8 hours, obtain at 100 DEG C
To compound macropore chlorine ball DZ-2.
Halogenated alkyl POSS compound is not used: 30 grams of compound macropore chlorine ball DZ-2 (chlorine being added in 500ml there-necked flask
Content is 2.8mmol Cl/g), N- methylimidazole (84.0mmol) and 200ml acetonitrile, reacts 24 hours, is cooled at 80 DEG C
Room temperature, filtering, is successively washed with ethyl acetate, the HCl of 0.1mol/L, deionized water, methanol, is then dried 12 hours for 60 DEG C of vacuum
Obtain compound imidazoles microballoon DZ-2.
In 1000ml three-necked flask, the phosphorus tungsten that 30 grams of compound imidazoles microballoon DZ-2,500ml concentration are 0.1mol/L is added
Progress ion-exchange reactions 24 hours is stirred at room temperature in the deionized water solution of sour sodium；It is then washed with deionized until washing
Liquid pH=7 obtains ion-exchange resin catalyst after vacuum drying, is denoted as Cat-DZ-2, and structural formula is as follows:
The preparation of [comparative example 3] comparative catalyst
Nano material is not added prepares macroporous microsphere: 47.0 grams of styrene of addition in 500 milliliters of three-necked flasks, 2.3 grams
260 millis for being dissolved with 2.0 grams of gelatin are added in divinylbenzene, 30 grams of polystyrene and 1.6 grams of benzoyl peroxide initiators
Rise deionized water solution.Mixing speed is adjusted, is stirred 2 hours.It is stirred to react at 60 DEG C 2.0 hours, is then gradually warming up to
It 80 DEG C, reacts 5 hours；It is warming up to 90 DEG C again, reacts 5 hours, is finally warming up to 98 DEG C, reacts 8 hours.After reaction, incline
Supernatant liquid is poured out, is washed with 85 DEG C of hot water, then washed with cold water, is then filtered, 80 DEG C of drying in baking oven is put into, is sieved, receive
Collect macroporous microsphere DZ-3 of the partial size within the scope of 0.35~0.60mm.
Macroporous microsphere chloromethylation: in the three-necked flask of 500ml, 40 grams of macroporous microsphere DZ-3 and 200ml chloromethanes are added
Ether is stored at room temperature 3 hours, starts to stir, and it is catalyst that 15 grams of zinc chloride, which are added, is warming up to 50 DEG C and reacts 12 hours, chloromethyl
It is cooled to room temperature after change, filters out chlorination mother solution, washed repeatedly with methanol, dried 8 hours at 100 DEG C, obtain macropore chlorine
Ball DZ-3.
30 grams of macropore chlorine ball DZ-3 (chlorinity is 2.9mmol Cl/g), imidazoles are added in 500ml there-necked flask
(87.0mmol) and 200ml acetonitrile, reacts 24 hours at 80 DEG C, are cooled to room temperature, and filter, successively use ethyl acetate,
The HCl of 0.1mol/L, deionized water, methanol washing, then 60 DEG C of vacuum bakings obtain imidazoles microballoon DZ-3 in 12 hours.
In 500ml three-necked flask, it is added 30 grams of imidazoles microballoon DZ-3 (imidazole group content is 2.6mmol/g), 7.9 grams
Eight chloromethyl silsesquioxanes and 300ml tetrahydrofuran filter after reaction 24 hours at 100 DEG C, with tetrahydro furan
Mutter, deionized water is successively washed, obtain imidazoles/POSS microballoon DZ-3.
In 1000ml three-necked flask, the phosphorus that 30 grams of imidazoles/POSS microballoon DZ-3,500ml concentration is 0.1mol/L is added
Progress ion-exchange reactions 24 hours is stirred at room temperature in the deionized water solution of sodium tungstate；Then be washed with deionized until
Washing lotion pH=7 obtains ion-exchange resin catalyst after vacuum drying, is denoted as Cat-DZ-3, and structural formula is as follows:
[embodiment 7] catalytic applications
The ion-exchange resin catalyst of [embodiment 1] preparation is used for the ester exchange reaction of grease and short chain alcohol, reaction
Condition is as follows: under inert gas protection, soybean oil and methanol being added in autoclave according to the molar ratio of 40:1, then
The 5% catalyst Cat-A1 that quality is soybean oil quality is added, 60 DEG C of reaction temperature are reacted 12 hours.It samples after reaction
Analysis measurement is carried out, the yield for measuring biodiesel is 96.3% (using the yield of fatty acid methyl ester as index).
[embodiment 8~14] catalytic applications
Change used in resin catalyst, and reaction temperature and time, remaining reaction condition all with [embodiment 7]
It is identical, the ester exchange reaction of grease and short chain alcohol is carried out, obtained reaction result is shown in Table 1.
Table 1
[embodiment 15] catalytic applications
Catalyst Cat-A1 used in [embodiment 7] is filtered, is washed, it is dry, then according to the anti-of [embodiment 7]
Step and reaction condition are answered, the ester exchange reaction of grease and short chain alcohol is catalyzed, obtains catalyst circulation using 2 times as a result, seeing
Table 2.The rest may be inferred, carries out the catalysis that cycle-index is 3~5 times respectively and reacts, the results are shown in Table 2.
Table 2
| Cycle-index | 2 | 3 | 4 | 5 |
| Biodiesel yield/% | 96.2 | 96.2 | 96.1 | 96.3 |
[comparative example 4-6] catalytic applications
The ion-exchange resin catalyst of [comparative example 1-3] preparation is used for the ester exchange reaction of grease and short chain alcohol.Instead
It answers condition as follows: under inert gas protection, soybean oil and methanol being added in autoclave according to the molar ratio of 40:1, with
5% comparative catalyst that quality is soybean oil quality is added afterwards, 60 DEG C of reaction temperature are reacted 12 hours.It samples after reaction
Analysis measurement is carried out, reaction result is as shown in table 3.
Table 3
[comparative example 7] catalytic applications
By catalyst filtration used in [comparative example 4-6], wash, it is dry, then according to the reaction of [comparative example 4-6]
Step and reaction condition are catalyzed the ester exchange reaction of grease and short chain alcohol, obtain catalyst circulation using 2 times as a result, being shown in Table
4.The rest may be inferred, carries out the catalysis that cycle-index is 3~5 times respectively and reacts, the results are shown in Table 4.
Table 4
Claims (10)
1. a kind of synthetic method of biodiesel, is included under the conditions of ester exchange reaction, grease and short chain alcohol and amberlite
The step of rouge catalyst contacts；The ion-exchange resin catalyst has following structure general formula:
Wherein,For macroporous type nanocomposite resin matrix；
M-For anion, it is selected from phosphotungstic acid root, phosphomolybdic acid root, silico-tungstic acid root, silicomolybdic acid root, arsenowolframic acid root, arsenic molybdate, germanium tungsten
Acid group, germanium molybdate, tungstovanadophosphoric acid root or molybdovanaphosphoric acid root；
POSS is cage-type silsesquioxane unit, and general formula is (- SiO1.5)m；M is 6,8,10 or 12；
For glyoxaline cation unit；
Linking group of the R between POSS unit and glyoxaline cation unit, R are alkylidene or arylene；
The macroporous type nanocomposite resin matrix is styrene monomer, comonomer, nano material and pore-foaming agent through original position
It is copolymerized obtained nanometer macroporous type copolymer；The nano material is selected from multi-walled carbon nanotube, single-walled carbon nanotube, C60 or C70
At least one of fullerene.
2. the synthetic method of biodiesel according to claim 1, which is characterized in that POSS unit is in the amberlite
Content in rouge catalyst is 2~8 weight %.
3. the synthetic method of biodiesel according to claim 1, which is characterized in that M-For phosphotungstic acid radical ion.
4. the synthetic method of biodiesel according to claim 1, which is characterized in that alkylidene is selected from methylene, ethylidene
Or propylidene；Arylene is selected from phenylene, naphthylene or sub- benzyl.
5. the synthetic method of biodiesel according to claim 1, which is characterized in that the styrene monomer is selected from benzene second
At least one of alkene, α-methylstyrene or 4- butylstyrene；
The comonomer is selected from ethyleneglycol dimethyacrylate, diallyl benzene, divinyl phenylmethane or divinyl
At least one of base benzene；
The pore-foaming agent be selected from aliphatic hydrocarbon, polystyrene, gasoline, poly- (propylene glycol), poly(ethylene glycol), dimethyl silicone polymer,
At least one of fatty acid or paraffin.
6. the synthetic method of biodiesel according to claim 5, which is characterized in that the styrene monomer is selected from benzene second
Alkene；The comonomer is selected from divinylbenzene；The pore-foaming agent is selected from polystyrene.
7. the synthetic method of biodiesel according to claim 1, which is characterized in that the nano material is selected from multi wall carbon and receives
Mitron.
8. the synthetic method of biodiesel according to claim 1, which is characterized in that the dosage of styrene monomer be 85~
95 parts, the dosage of comonomer is 2~5 parts, and the dosage of nano material is 0.1~3 part, and the dosage of pore-foaming agent is 10~100 parts.
9. the synthetic method of biodiesel according to claim 1, which is characterized in that the grease is selected from fatty glyceride
Any one of vegetable and animals oils；The short chain alcohol is any in methanol, ethyl alcohol, propyl alcohol or butanol.
10. the synthetic method of biodiesel according to claim 1, which is characterized in that the ester exchange reaction condition includes:
Short chain alcohol and the molar ratio of grease are (10~50): 1, catalyst amount is the 1~15% of raw oil material quality, reaction temperature 40
~180 DEG C, the reaction time 1~24 hour.
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| CN101418225A (en) * | 2007-10-23 | 2009-04-29 | 北京化工大学 | Method for preparing biodiesel by using supported solid acid combining cosolvent |
| CN105924464A (en) * | 2016-05-18 | 2016-09-07 | 上海大学 | Octa-imidazolyl POSS room temperature ionic liquid and preparation method thereof |
| CN106391114A (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 |
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| CN101418225A (en) * | 2007-10-23 | 2009-04-29 | 北京化工大学 | Method for preparing biodiesel by using supported solid acid combining cosolvent |
| CN106391114A (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 |
| CN105924464A (en) * | 2016-05-18 | 2016-09-07 | 上海大学 | Octa-imidazolyl POSS room temperature ionic liquid and preparation method thereof |
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| Title |
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| JING WANG等: "Electrostatic immobilization of phosphomolybdic acid on imidazolium-based mesoporous organosilicas for catalytic olefin expoxidatio", 《催化学报》 * |
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