CN109777626B - Method for producing biodiesel - Google Patents
Method for producing biodiesel Download PDFInfo
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- CN109777626B CN109777626B CN201711111507.4A CN201711111507A CN109777626B CN 109777626 B CN109777626 B CN 109777626B CN 201711111507 A CN201711111507 A CN 201711111507A CN 109777626 B CN109777626 B CN 109777626B
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Abstract
The invention relates to a method for producing biodiesel, which comprises the steps of contacting grease and short-chain alcohol with an ion exchange resin catalyst under the condition of ester exchange reaction; the ion exchange resin catalyst has the following structural general formula:
wherein the content of the first and second substances,
is a gel type nano composite resin matrix; m‑Is an anion selected from phosphotungstate, phosphomolybdate, silicotungstate, silicomolybdate, arsenic tungstate, arsenic molybdate, germanium tungstate, germanium molybdate, phosphotungstate, phosphomolybdate vanadate, or phosphomolybdate vanadate; POSS is a cage type silsesquioxane unit;
Description
Technical Field
The invention relates to a production method of biodiesel.
Background
With the continuous consumption of traditional fossil energy, people are increasingly urgent to research and develop new green and renewable energy. The traditional fossil fuel can generate sulfur dioxide, nitrogen oxide and other large amount of dust in the combustion process, thereby causing great harm to the ecological environment. And the biodiesel is used as a green energy source, and compared with petroleum diesel, the biodiesel has the characteristics of reproducibility, biodegradability, low waste discharge, high cetane number, high flash point, safe use and the like.
The preparation method of the biodiesel mainly comprises a direct use method, a mixed use method, a micro-emulsion method, a high-temperature cracking method and an ester exchange method. At present, the ester exchange method is used in industry, which uses oil crops such as soybean, rape, cotton, palm, and the like, aquatic plant oil and fat such as wild oil plants, engineering microalgae, and the like, animal oil and fat, food and beverage waste oil, and the like as raw material oil, and the raw material oil and short-chain alcohol are prepared into fatty acid methyl ester substances through an ester exchange or thermochemical process to replace petroleum diesel.
The ester exchange method is used for preparing biodiesel by adopting a plurality of methods, such as a homogeneous acid-base method, a lipase method, a supercritical method, a heterogeneous acid-base method and the like. The traditional homogeneous acid-base catalysis method has the problems of equipment corrosion, complex post-treatment, generation of a large amount of three wastes and the like; the enzyme catalyst in the lipase method is concerned by a lot of attention due to environmental friendliness, but the enzyme catalysis needs longer reaction time and is easy to inactivate, and meanwhile, the use amount of the enzyme catalyst is larger, so that the wide application of the enzyme catalyst is limited; the supercritical method for preparing the biodiesel has high conversion rate, but needs high-temperature and high-pressure conditions, and has high equipment requirement and high energy consumption; although the heterogeneous acid-base catalysis method has convenient catalyst recovery, the method also has low reaction activity and certain limitation. Therefore, the development of environment-friendly high-efficiency catalysts becomes a current research hotspot.
The acidic ionic liquid is used as a novel environment-friendly solvent and a high-efficiency catalyst, simultaneously has high-density reaction active sites of a traditional liquid acid catalyst and non-volatility of solid acid, and is considered to be one of the most promising green catalysts due to designability of the molecular structure and acidity of the acidic ionic liquid. However, the acidic ionic liquid has the disadvantages of high viscosity, high cost and inconvenient product/catalyst separation, so that the acidic ionic liquid is greatly limited in the industrial process of catalyzing biodiesel.
Document CN201410442179.6 discloses a method for preparing N-methyl-N-alkyl morpholine type ionic liquid, which is used as a catalyst for preparing biodiesel by transesterification of biolipid and methanol, and has high activity, low dosage and stable performance. The yield of the biodiesel can reach 93.7 percent when the reaction is carried out for 1 hour at the temperature of 60 ℃ under the condition that the ratio of methanol to soybean oil alcohol oil is 40.
The immobilized ionic liquid combines the advantages of high activity of a homogeneous catalyst, easy separation and recovery of the heterogeneous catalyst and the like, is a novel green catalyst, and has great application potential in the field of biodiesel synthesis.
Document CN201510064336.9 discloses an acidic ionic liquid solid-planting catalyst for synthesizing biodiesel, which is prepared by solid-planting an ionic liquid [2-MPYR-BS ] [ HSO4], [ HMIM-BS ] [ HSO4] or [ PYR-BS ] [ HSO4] onto a mesoporous molecular sieve Al-MCM-41 into which Al is introduced by an impregnation method to prepare a solid-planting ionic liquid catalyst, which is used for preparing biodiesel by an ester exchange method. Al-MCM-41- [2-MPYR-BS ] [ HSO4] is used as a catalyst, and the reaction is carried out for 6 hours at 150 ℃ under a certain alcohol-oil ratio, so that the yield of the biodiesel can reach 97.0%. The biodiesel does not need neutralization and washing, is environment-friendly, and the catalyst has excellent catalytic activity and is easy to recover. However, the solid-planted ionic liquid catalyst prepared by the impregnation method still has a certain problem of loss of active centers, and after the catalyst is used for 5 times, the yield of the biodiesel is reduced to 91.5%, and the reusability is poor.
Document CN201710337145.4 discloses a method for preparing a solid base catalyst special for biodiesel, wherein a polymer emulsion is used to adsorb potassium bicarbonate, and two-step calcination is performed to form a spongy porous solid base catalyst, wherein both a carrier and active ingredients are porous structures, although the problem that the pore channels of the catalyst prepared by the traditional impregnation method are easy to block is solved. But the reusability of the catalyst is poor, and after 5 times of reusability, the yield of the biodiesel is reduced from 94.6% to 88.9%.
The catalytic activity of the supported ionic liquid catalyst depends not only on the properties of the ionic liquid itself, but also on various properties of the carrier, such as heat resistance, solvent resistance, porosity, and the like. Therefore, it is very important to design a transesterification catalyst for preparing biodiesel with high activity and excellent recycling performance.
Disclosure of Invention
The invention provides a production method of biodiesel. The method comprises the steps of contacting grease and short-chain alcohol with an ion exchange resin catalyst under ester exchange reaction conditions; the ion exchange resin catalyst has the following structural general formula:
wherein the content of the first and second substances,
is a gel type nano composite resin matrix;
M-is an anion selected from phosphotungstate, phosphomolybdate, silicotungstate, silicomolybdate, arsenic tungstate, arsenic molybdate, germanium tungstate, germanium molybdate, phosphotungstate, phosphomolybdate vanadate, or phosphomolybdate vanadate;
POSS is a cage-type silsesquioxane unit with the general formula of (-SiO)1.5)m(ii) a m is 6, 8, 10 or 12;
r is a connecting group between the POSS unit and the imidazole cation unit, and R is alkylene or arylene;
the gel type nano composite resin matrix is a nano gel type copolymer obtained by in-situ copolymerization of styrene monomers, comonomers and nano materials; the nano material is at least one of multi-wall carbon nano tube, single-wall carbon nano tube, C60 or C70 fullerene.
According to one aspect of the invention, the POSS units are present in the ion exchange resin in an amount of 2 to 8 wt.%.
According to one aspect of the invention, M-Is phosphotungstic acid radical ion.
According to one aspect of the invention, the alkylene group is selected from methylene, ethylene or propylene; the arylene group is selected from phenylene, naphthylene or phenylmethyl.
According to one aspect of the invention, the styrenic monomer is selected from at least one of styrene, alpha-methylstyrene or 4-butylstyrene, preferably styrene.
According to one aspect of the invention, the comonomer is selected from at least one of ethylene glycol dimethacrylate, diacrylene, divinylphenylmethane or divinylbenzene, preferably divinylbenzene.
According to one aspect of the invention, the nanomaterial is preferably a multi-walled carbon nanotube.
According to one aspect of the invention, the styrene monomer is 85-95 parts, the comonomer is 2-5 parts, and the nanomaterial is 0.1-3 parts.
According to an aspect of the present invention, the fat is any one selected from animal and vegetable oils of fatty acid glyceride. Such as vegetable oil such as soybean oil, rapeseed oil, cottonseed oil or palm oil, aquatic plant oil such as wild plant oil and engineering microalgae, animal oil and food waste oil, etc.
According to one aspect of the invention, the short-chain alcohol is selected from any one of methanol, ethanol, propanol or butanol.
According to one aspect of the invention, the transesterification reaction conditions include: the molar ratio of the short-chain alcohol to the oil ester is (10-50): 1, the amount of the catalyst is 1-15% of the mass of the raw material grease, the reaction temperature is 40-180 ℃, and the reaction time is 1-24 hours.
The preparation method of the ion exchange resin catalyst comprises the following steps:
a) preparing an auxiliary agent into an aqueous solution A with the weight percentage concentration of 0.5-2%, and preparing a styrene monomer, a comonomer, a nano material and an initiator into a solution B; wherein, the styrene monomer is selected from at least one of styrene, alpha-methyl styrene or 4-butyl styrene; the comonomer is selected from at least one of ethylene glycol dimethacrylate, diacrylene, divinyl phenyl methane or divinyl benzene; the nano material is selected from at least one of multi-wall carbon nano tubes, single-wall carbon nano tubes, C60 or C70 fullerene; the initiator is selected from at least one of benzoyl peroxide, azobisisobutyronitrile, lauroyl peroxide or cumene hydroperoxide; the auxiliary agent is selected from at least one of polyvinyl alcohol, gelatin, starch, methyl cellulose, bentonite or calcium carbonate; the weight parts of the styrene monomer, the comonomer, the nano material and the initiator are 85-95 parts, 2-5 parts, 0.1-3 parts and 0.1-10 parts respectively; the dosage of the auxiliary agent is 150-400% of the dosage of the monomer;
b) pre-polymerizing the solution B at 60-75 ℃ for 0.5-2.5 hours, then mixing the solution B with the solution A, heating to 70-90 ℃ for reaction for 5-15 hours, and heating to 90-100 ℃ for reaction for 5-15 hours; after the reaction is finished, extracting, washing, filtering, drying and sieving to obtain composite gel microspheres with the particle size range of 0.35-0.60 mm;
c) chloromethylating the composite gel microspheres: adding a chloromethylation reagent which is 200-500% of the weight of the composite gel microsphere and a zinc chloride catalyst which is 20-70% of the weight of the composite gel microsphere into the composite gel microsphere, reacting for 8-30 hours at 30-60 ℃, filtering and washing to obtain a composite gel chlorine ball; the chloromethylation reagent is selected from at least one of chloromethyl ether, chloroethyl ether or 1, 4-dichloromethoxybutane;
d) reacting the mixture of the composite gel chlorine spheres, imidazole and acetonitrile at 60-90 ℃ to obtain composite imidazole microspheres; in the mixture, the mol ratio of the composite gel chlorine ball to the imidazole to the acetonitrile is 1: (1-2): (30-150);
e) mixing the composite imidazole microspheres and alkyl halogenated POSS compounds according to the equimolar ratio of imidazole functional groups and halogenated functional groups, dissolving the mixture in tetrahydrofuran, filtering the mixture after the reaction is finished at 100 ℃ for 24-72 hours, and washing the mixture to obtain the composite imidazole/POSS microspheres; the alkyl halogenated POSS compound is selected from at least one of octachloromethyl POSS, octachloroethyl POSS and octachloropropyl POSS;
f) and washing the composite imidazole/POSS microspheres by using a salt solution, wherein the molar ratio of the composite imidazole/POSS microspheres to the salt solution is (1: 1) to (1: 10) (ii) a The concentration of the salt solution is 0.1-1 mol/L; and after washing, washing the product with deionized water until the pH value is 7 to obtain the ion exchange resin. The salt solution is at least one of phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, silicomolybdic acid, arsenic tungstic acid, arsenic molybdic acid, germanium tungstic acid, germanium molybdic acid, phosphotungstic acid and phosphomolybdovanadic acid solution.
The invention has the beneficial effects that: the ion exchange resin catalyst of the present invention contains two different nanomaterials: nanocarbon materials and Polyhedral silsesquioxanes (POSS for short). Under the action of an initiator, the nano carbon material, the monomer and the comonomer are introduced into the resin matrix through in-situ polymerization, so that the glass transition temperature of the resin matrix is increased; meanwhile, due to the introduction of the nano carbon material, the swelling resistance of the resin matrix is improved. And the POSS comprises an inorganic support structure consisting of Si and O, so that the ion exchange resin is endowed with good heat resistance, and the thermal stability is obviously improved.
The preferred scheme of the invention is that chloromethylated styrene, divinyl benzene and multi-walled carbon nano-tube in-situ gel type copolymer resin matrix reacts with imidazole to obtain composite imidazole microspheres, then the imidazole groups react with alkyl halogenated POSS compounds, and finally the composite imidazole microspheres undergo ion exchange reaction with salt solution to prepare the gel type ion exchange resin containing two different nano materials. Covalent bonding of the carbon nanotubes and the polymer matrix is realized through in-situ copolymerization between the carbon nanotubes and the monomers and comonomers, and bonding between the POSS and the resin matrix is realized through chemical reaction of halogenated alkylated POSS compounds and imidazole groups.
The gel type ion exchange resin catalyst containing two different nano materials is used for the ester exchange reaction of grease and short chain alcohol, and has the following advantages:
(1) the prepared catalyst is used for preparing biodiesel by an ester exchange method, and has high catalytic activity;
(2) the catalyst is easy to recover, has good stability and can be repeatedly used.
The invention is further illustrated by the following examples, but it is to be noted that the scope of the invention is not limited thereto, but is defined by the appended claims.
It should be particularly noted that two or more aspects (or embodiments) disclosed in the context of the present specification may be combined with each other at will, and thus form part of the original disclosure of the specification, and also fall within the scope of the present invention.
Detailed Description
[ example 1 ] preparation of ion exchange resin catalyst
47.0 g of styrene, 2.3 g of divinylbenzene and 1.6 g of benzoyl peroxide initiator are added into a 500ml three-neck flask, and stirred and reacted for 2.0 hours at the temperature of 60 ℃; then 0.6 g of multi-walled carbon nanotubes was added and stirring was continued for 1 hour for prepolymerization. A solution of 2.0 g of gelatin dissolved in 260 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water at 85 ℃, washing with cold water, filtering, drying in an oven at 80 ℃, sieving, and collecting the composite gel microspheres A1 with the particle size of 0.35-0.60 mm.
Chloromethylation of composite gel microspheres: adding 40 g of composite gel microsphere A1 and 250ml of chloromethyl ether into a 500ml three-neck flask, standing at room temperature for 3 hours, starting stirring, adding 10 g of zinc chloride as a catalyst, heating to 60 ℃ for reaction for 10 hours, cooling to room temperature after chloromethylation is finished, filtering out chlorinated mother liquor, repeatedly washing with methanol, and drying at 100 ℃ for 8 hours to obtain the composite gel microsphere A1.
30 g of composite gel chlorine ball A1 (chlorine content is 3.5mmol Cl/g), imidazole (105.0mmol) and 200ml of acetonitrile are added into a 500ml three-neck flask, and the mixture reacts for 24 hours at 60 ℃, is cooled to room temperature, is filtered, is washed by ethyl acetate, 0.1mol/L HCl, deionized water and methanol in sequence, and is dried for 24 hours at 60 ℃ in vacuum to obtain the composite imidazole microsphere A1.
30 g of composite imidazole microsphere A1 (imidazole group content is 3.1mmol/g), 9.8 g of octachloromethyl silsesquioxane and 300ml of tetrahydrofuran are added into a 500ml three-neck flask, and after the reaction is finished, the mixture is filtered and washed by tetrahydrofuran and deionized water in sequence at 100 ℃ for 24 hours to obtain the composite imidazole/POSS microsphere A1.
Adding 30 g of composite imidazole/POSS microspheres A1 and 500ml of deionized water solution of sodium phosphotungstate with the concentration of 0.1mol/L into a 1000ml three-neck flask, and stirring at room temperature to perform ion exchange reaction for 24 hours; then washing the catalyst by deionized water until the pH value of washing liquor is 7, and drying the catalyst in vacuum to obtain the ion exchange resin catalyst of two different nano materials, which is marked as Cat-A1, wherein the POSS unit content is 4.1 percent, and the structural formula is as follows:
[ example 2 ] preparation of ion exchange resin catalyst
A monomer mixture solution containing an initiator (60.0 g of styrene, 1.0 g of divinyl benzene, 1.6 g of multi-walled carbon nano-tube and 1.0 g of benzoyl peroxide are added into a 500ml three-neck flask, the solution is stirred and reacted for 0.5 hour at 70 ℃, a stirrer is started, a mixed solution of 200ml of deionized water and 4 g of polyvinyl alcohol is added, the temperature is raised to 85 ℃, the reaction is carried out for 3 hours, the temperature is raised to 90 ℃, the reaction is carried out for 9 hours, and finally the temperature is raised to 100 ℃ and the reaction is carried out for 10 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water at 85 ℃, washing with cold water, filtering, drying in an oven at 80 ℃, sieving, and collecting the composite gel microspheres B1 with the particle size of 0.35-0.60 mm.
Chloromethylation of the composite microsphere: adding 50 g of composite microsphere B1 and 200ml of chloroethyl ether into a 500ml three-neck flask, standing at room temperature for 6 hours, adding 30 g of zinc chloride serving as a catalyst, starting stirring, heating to 50 ℃ for reaction for 30 hours, cooling to room temperature after chloromethylation is finished, filtering out a chlorination mother solution, repeatedly washing with methanol, and drying at 100 ℃ for 8 hours to obtain the composite gel chlorine sphere B1.
50 g of composite gel chlorine ball B1 (the chlorine content is 4.5mmol Cl/g), imidazole (225.0mmol) and 300ml of acetonitrile are added into a 500ml three-neck flask, the mixture reacts for 16 hours at 80 ℃, the mixture is cooled to room temperature, filtered, washed by ethyl acetate, 0.1mol/L HCl, deionized water and methanol in sequence, and then dried for 24 hours at 60 ℃ in vacuum to obtain the composite imidazole microsphere B1.
50 g of composite imidazole microsphere B1 (the imidazole group content is 3.9mmol/g), 21.0 g of octachloromethyl silsesquioxane and 500ml of tetrahydrofuran are added into a 1000ml three-neck flask, and after the reaction is finished, the mixture is filtered and washed by tetrahydrofuran and deionized water in sequence at 100 ℃ for 72 hours to obtain the composite imidazole/POSS microsphere B1.
Adding 40 g of composite imidazole/POSS microspheres B1 and 400ml of deionized water solution of sodium phosphotungstate with the concentration of 1.0mol/L into a 1000ml three-neck flask, and stirring at room temperature to perform ion exchange reaction for 24 hours; then washing with deionized water until the pH value of washing liquor is 7, and drying in vacuum to obtain the ion exchange resin catalyst of two different nano materials, namely Cat-B1, wherein the POSS unit content is 4.3%, and the structural formula is as follows:
[ example 3 ] preparation of ion exchange resin catalyst
A monomer mixture solution containing an initiator (42.5 g of styrene, 2.5 g of divinyl benzene, 0.1 g of multi-walled carbon nano tube and 2.0 g of benzoyl peroxide are added into a 500ml three-neck flask, the solution is stirred and reacted for 1.5 hours at 70 ℃, 200ml of a mixed solution of deionized water and 4 g of polyvinyl alcohol is added, the temperature is increased to 85 ℃, the reaction is carried out for 3 hours, the temperature is increased to 90 ℃, the reaction is carried out for 9 hours, and finally the temperature is increased to 100 ℃, and the reaction is carried out for 10 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water at 85 ℃, washing with cold water, filtering, drying in an oven at 80 ℃, sieving, and collecting the composite gel microspheres C1 with the particle size of 0.35-0.60 mm.
Chloromethylation of the composite microspheres: adding 20 g of composite microsphere C1 and 100 ml of 1, 4-dichloromethoxybutane into a 250ml three-neck flask, standing for 6 hours at room temperature, adding 8 g of zinc chloride as a catalyst, starting stirring, heating to 30 ℃ for reaction for 24 hours, cooling to room temperature after chloromethylation is finished, filtering out chlorinated mother liquor, repeatedly washing with methanol, and drying for 8 hours at 100 ℃ to obtain the composite gel chlorine sphere C1.
20 g of composite gel chlorine sphere C1 (chlorine content is 1.45mmol Cl/g), imidazole (34.0mmol) and 150ml of acetonitrile are added into a 250ml three-neck flask, the mixture reacts for 16 hours at 90 ℃, the mixture is cooled to room temperature and filtered, and the mixture is washed by ethyl acetate, 0.1mol/L HCl, deionized water and methanol in sequence and then dried for 24 hours at 60 ℃ in vacuum to obtain the composite imidazole microsphere C1.
20 g of composite imidazole microsphere C1 (the content of imidazole groups is 1.6mmol/g), 3.7 g of octachloroethyl silsesquioxane and 150ml of tetrahydrofuran are added into a 250ml three-neck flask, and after the reaction is finished, filtration is carried out for 72 hours at 100 ℃, and then the mixture is washed by tetrahydrofuran and deionized water in sequence to obtain the composite imidazole/POSS microsphere C1.
Adding 20 g of composite imidazole/POSS microsphere C1 and 300ml of deionized water solution of sodium phosphotungstate with the concentration of 0.5mol/L into a 500ml three-neck flask, and stirring at room temperature to perform ion exchange reaction for 24 hours; then washing with deionized water until the pH value of washing liquor is 7, and drying in vacuum to obtain the ion exchange resin catalyst of two different nano materials, which is recorded as Cat-C1, wherein the POSS unit content is 3.3%, and the structural formula is as follows:
[ example 4] preparation of ion exchange resin catalyst
47.0 g of styrene, 2.3 g of divinylbenzene and 1.6 g of benzoyl peroxide initiator are added into a 500ml three-neck flask, and stirred and reacted for 2.0 hours at the temperature of 60 ℃; then 0.6 g of single-walled carbon nanotubes was added and stirring was continued for 1 hour for prepolymerization. A solution of 2.0 g of gelatin dissolved in 260 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water at 85 ℃, washing with cold water, filtering, drying in an oven at 80 ℃, sieving, and collecting the composite gel microspheres A2 with the particle size of 0.35-0.60 mm.
Chloromethylation of composite gel microspheres: adding 40 g of composite gel microsphere A2 and 250ml of chloromethyl ether into a 500ml three-neck flask, standing at room temperature for 3 hours, starting stirring, adding 10 g of zinc chloride as a catalyst, heating to 60 ℃ for reaction for 10 hours, cooling to room temperature after chloromethylation is finished, filtering out chlorinated mother liquor, repeatedly washing with methanol, and drying at 100 ℃ for 8 hours to obtain the composite gel microsphere A2.
30 g of composite gel chlorine ball A2 (chlorine content is 3.3mmol Cl/g), imidazole (99.0mmol) and 200ml of acetonitrile are added into a 500ml three-neck flask, the mixture reacts for 24 hours at 60 ℃, the mixture is cooled to room temperature and filtered, and the mixture is washed by ethyl acetate, 0.1mol/L HCl, deionized water and methanol in sequence and then dried for 24 hours at 60 ℃ in vacuum to obtain the composite imidazole microsphere A2.
30 g of composite imidazole microsphere A2 (imidazole group content is 3.0mmol/g), 9.2 g of octachloromethyl silsesquioxane and 300ml of tetrahydrofuran are added into a 500ml three-neck flask, and after the reaction is finished, the mixture is filtered and washed by tetrahydrofuran and deionized water in sequence at 100 ℃ for 24 hours to obtain the composite imidazole/POSS microsphere A2.
Adding 30 g of composite imidazole/POSS microspheres A2 and 500ml of deionized water solution of sodium phosphotungstate with the concentration of 0.1mol/L into a 1000ml three-neck flask, and stirring at room temperature to perform ion exchange reaction for 24 hours; then washing the catalyst by deionized water until the pH value of washing liquor is 7, and drying the catalyst in vacuum to obtain the ion exchange resin catalyst of two different nano materials, which is marked as Cat-A2, wherein the POSS unit content is 4.0 percent, and the structural formula is as follows:
[ example 5 ] preparation of ion exchange resin catalyst
A monomer mixture solution containing an initiator (60.0 g of styrene, 1.0 g of divinyl benzene, 1.6 g of single-walled carbon nanotube and 1.0 g of benzoyl peroxide are added into a 500ml three-neck flask, the solution is stirred and reacted for 0.5 hour at 70 ℃, a stirrer is started, a mixed solution of 200ml of deionized water and 4 g of polyvinyl alcohol is added, the temperature is increased to 85 ℃, the reaction is carried out for 3 hours, the temperature is increased to 90 ℃, the reaction is carried out for 9 hours, and finally the temperature is increased to 100 ℃, and the reaction is carried out for 10 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water at 85 ℃, washing with cold water, filtering, drying in an oven at 80 ℃, sieving, and collecting the composite gel microspheres B2 with the particle size of 0.35-0.60 mm.
Chloromethylation of the composite microspheres: adding 50 g of composite microsphere B2 and 200ml of chloroethyl ether into a 500ml three-neck flask, standing at room temperature for 6 hours, adding 30 g of zinc chloride serving as a catalyst, starting stirring, heating to 50 ℃ for reaction for 30 hours, cooling to room temperature after chloromethylation is finished, filtering out a chlorination mother solution, repeatedly washing with methanol, and drying at 100 ℃ for 8 hours to obtain the composite gel chlorine sphere B2.
50 g of composite gel chlorine ball B2 (the chlorine content is 4.9mmol Cl/g), imidazole (245.0mmol) and 300ml of acetonitrile are added into a 500ml three-neck flask, the mixture reacts for 16 hours at 80 ℃, the mixture is cooled to room temperature, filtered, washed by ethyl acetate, 0.1mol/L HCl, deionized water and methanol in sequence, and then dried for 24 hours at 60 ℃ in vacuum to obtain the composite imidazole microsphere B2.
50 g of composite imidazole microsphere B2 (the content of imidazole groups is 4.2mmol/g), 21.3 g of octachloromethylsilsesquioxane and 500ml of tetrahydrofuran are added into a 1000ml three-neck flask, and after the reaction is finished, the mixture is filtered and washed by tetrahydrofuran and deionized water in sequence, so that the composite imidazole/POSS microsphere B2 is obtained.
Adding 40 g of composite imidazole/POSS microspheres B2 and 400ml of deionized water solution of sodium phosphotungstate with the concentration of 1.0mol/L into a 1000ml three-neck flask, and stirring at room temperature to perform ion exchange reaction for 24 hours; then washing the catalyst by deionized water until the pH value of washing liquor is 7, and drying the catalyst in vacuum to obtain the ion exchange resin catalyst of two different nano materials, which is marked as Cat-B2, wherein the POSS unit content is 4.4%, and the structural formula is as follows:
[ example 6 ] preparation of ion exchange resin catalyst
A monomer mixture solution containing an initiator (42.5 g of styrene, 2.5 g of divinylbenzene, 0.1 g of single-walled carbon nanotube and 2.0 g of benzoyl peroxide are added into a 500ml three-neck flask, and the solution is stirred and reacted for 1.5 hours at 70 ℃, 200ml of a mixed solution of deionized water and 4 g of polyvinyl alcohol is added, the temperature is increased to 85 ℃, the reaction is carried out for 3 hours, then the temperature is increased to 90 ℃, the reaction is carried out for 9 hours, and finally the temperature is increased to 100 ℃, and the reaction is carried out for 10 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water at 85 ℃, washing with cold water, filtering, drying in an oven at 80 ℃, sieving, and collecting the composite gel microspheres C2 with the particle size of 0.35-0.60 mm.
Chloromethylation of the composite microspheres: adding 20 g of composite microsphere C2 and 100 ml of 1, 4-dichloromethoxybutane into a 250ml three-neck flask, standing for 6 hours at room temperature, adding 8 g of zinc chloride as a catalyst, starting stirring, heating to 30 ℃ for reaction for 24 hours, cooling to room temperature after chloromethylation is finished, filtering out chlorinated mother liquor, repeatedly washing with methanol, and drying for 8 hours at 100 ℃ to obtain the composite gel chlorine sphere C2.
20 g of composite gel chlorine sphere C2 (chlorine content is 1.6mmol Cl/g), imidazole (32.0mmol) and 150ml of acetonitrile are added into a 250ml three-neck flask, the mixture reacts for 16 hours at 90 ℃, the mixture is cooled to room temperature and filtered, and the mixture is washed by ethyl acetate, 0.1mol/L HCl, deionized water and methanol in sequence and then dried for 24 hours at 60 ℃ in vacuum to obtain the composite imidazole microsphere C2.
20 g of composite imidazole microsphere C2 (the content of imidazole groups is 1.5mmol/g), 3.6 g of octachloroethyl silsesquioxane and 150ml of tetrahydrofuran are added into a 250ml three-neck flask, and after the reaction is finished, filtration is carried out for 72 hours at 100 ℃, and then the mixture is washed by tetrahydrofuran and deionized water in sequence to obtain the composite imidazole/POSS microsphere C2.
Adding 20 g of composite imidazole/POSS microsphere C2 and 300ml of deionized water solution of sodium phosphotungstate with the concentration of 0.5mol/L into a 500ml three-neck flask, and stirring at room temperature to perform ion exchange reaction for 24 hours; then washing the catalyst by deionized water until the pH value of washing liquor is 7, and drying the catalyst in vacuum to obtain the ion exchange resin catalyst of two different nano materials, which is marked as Cat-C2, wherein the POSS unit content is 3.2%, and the structural formula is as follows:
comparative example 1 preparation of comparative catalyst
Preparing gel microspheres without adding nano materials: a500 mL three-necked flask was charged with 47.0 grams of styrene, 2.3 grams of divinylbenzene and 1.6 grams of benzoyl peroxide initiator. A solution of 2.0 g gelatin dissolved in 260 ml of deionized water was added. The stirring speed was adjusted and the mixture was stirred for 2 hours. Stirring and reacting for 2.0 hours at 60 ℃, then gradually heating to 80 ℃, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water at 85 ℃, washing with cold water, filtering, drying in an oven at 80 ℃, sieving, and collecting the gel microspheres DZ-1 with the particle size of 0.35-0.60 mm.
Chloromethylation of gel microspheres: adding 40 g of gel microsphere DZ-1 and 250ml of chloromethyl ether into a 500ml three-neck flask, standing at room temperature for 3 hours, starting stirring, adding 10 g of zinc chloride as a catalyst, heating to 60 ℃ for reaction for 10 hours, cooling to room temperature after chloromethylation is finished, filtering out a chlorination mother solution, repeatedly washing with methanol, and drying at 100 ℃ for 8 hours to obtain the gel microsphere DZ-1.
Without the use of haloalkylated POSS compounds: 30 g of gel chlorine ball DZ-1 (the chlorine content is 3.6mmol Cl/g), N-methylimidazole (108.0mmol) and 200ml of acetonitrile are added into a 500ml three-neck flask, the mixture reacts for 24 hours at the temperature of 60 ℃, the mixture is cooled to room temperature and filtered, and then ethyl acetate, 0.1mol/L HCl, deionized water and methanol are sequentially used for washing, and then the mixture is dried for 24 hours at the temperature of 60 ℃ in vacuum to obtain the imidazole microsphere DZ-1.
Adding 30 g of imidazole microsphere DZ-1 and 500ml of deionized water solution of sodium phosphotungstate with the concentration of 0.1mol/L into a 1000ml three-neck flask, and stirring at room temperature to perform ion exchange reaction for 24 hours; followed by deionized water washing until the wash pH was 7, and drying in vacuo afforded the ion exchange resin catalyst, noted Cat-DZ-1:
comparative example 2 preparation of comparative catalyst
47.0 g of styrene, 2.3 g of divinylbenzene and 1.6 g of benzoyl peroxide initiator are added into a 500ml three-neck flask, and stirred and reacted for 2.0 hours at the temperature of 60 ℃; then 0.6 g of multi-walled carbon nanotubes was added and stirring was continued for 1 hour for prepolymerization. A solution of 2.0 g of gelatin dissolved in 260 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water at 85 ℃, washing with cold water, filtering, drying in an oven at 80 ℃, sieving, and collecting the composite gel microspheres DZ-2 with the particle size of 0.35-0.60 mm.
Chloromethylation of composite gel microspheres: adding 40 g of composite gel microsphere DZ-2 and 250ml of chloromethyl ether into a 500ml three-neck flask, standing for 3 hours at room temperature, starting stirring, adding 10 g of zinc chloride as a catalyst, heating to 60 ℃ for reaction for 10 hours, cooling to room temperature after chloromethylation is finished, filtering out chlorinated mother liquor, repeatedly washing with methanol, and drying for 8 hours at 100 ℃ to obtain the composite gel microsphere DZ-2.
Without the use of haloalkylated POSS compounds: 30 g of composite gel chlorine ball DZ-2 (the chlorine content is 3.5mmol Cl/g), N-methylimidazole (105.0mmol) and 200ml of acetonitrile are added into a 500ml three-neck flask, the mixture reacts for 24 hours at the temperature of 60 ℃, the mixture is cooled to room temperature and filtered, and then ethyl acetate, 0.1mol/L HCl, deionized water and methanol are sequentially used for washing, and then the mixture is dried for 24 hours at the temperature of 60 ℃ in vacuum to obtain the composite imidazole microsphere DZ-2.
Adding 30 g of composite imidazole microsphere DZ-2 and 500ml of deionized water solution of sodium phosphotungstate with the concentration of 0.1mol/L into a 1000ml three-neck flask, and stirring at room temperature to perform ion exchange reaction for 24 hours; followed by deionized water washing until the wash pH was 7, and drying in vacuo afforded the ion exchange resin catalyst, noted Cat-DZ-2:
comparative example 3 preparation of comparative catalyst
Preparing gel microspheres without adding nano materials: a500 mL three-necked flask was charged with 47.0 grams of styrene, 2.3 grams of divinylbenzene and 1.6 grams of benzoyl peroxide initiator. A solution of 2.0 g of gelatin dissolved in 260 ml of deionized water was added. The stirring speed was adjusted and the mixture was stirred for 2 hours. Stirring and reacting for 2.0 hours at 60 ℃, then gradually heating to 80 ℃, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water at 85 ℃, washing with cold water, filtering, drying in an oven at 80 ℃, sieving, and collecting the gel microspheres DZ-3 with the particle size of 0.35-0.60 mm.
Chloromethylation of gel microspheres: adding 40 g of gel microsphere DZ-3 and 250ml of chloromethyl ether into a 500ml three-neck flask, standing at room temperature for 3 hours, starting stirring, adding 10 g of zinc chloride as a catalyst, heating to 60 ℃ for reaction for 10 hours, cooling to room temperature after chloromethylation is finished, filtering out a chlorination mother solution, repeatedly washing with methanol, and drying at 100 ℃ for 8 hours to obtain the gel microsphere DZ-3.
30 g of gel chlorine ball DZ-3 (the chlorine content is 3.6mmol Cl/g), imidazole (108.0mmol) and 200ml of acetonitrile are added into a 500ml three-neck flask, the mixture reacts for 24 hours at the temperature of 60 ℃, the mixture is cooled to the room temperature and filtered, and then the mixture is washed by ethyl acetate, 0.1mol/L HCl, deionized water and methanol in sequence and then dried for 24 hours at the temperature of 60 ℃ in vacuum to obtain the imidazole microsphere DZ-3.
30 g of imidazole microsphere DZ-3 (the content of imidazole groups is 3.2mmol/g), 10.1 g of octachloromethylsilsesquioxane and 300ml of tetrahydrofuran are added into a 500ml three-neck flask, and the mixture is filtered after the reaction is finished at 100 ℃ and is washed by tetrahydrofuran and deionized water in sequence to obtain the imidazole/POSS microsphere DZ-3.
Adding 30 g of imidazole/POSS microsphere DZ-3 and 500ml of deionized water solution of sodium phosphotungstate with the concentration of 0.1mol/L into a 1000ml three-neck flask, and stirring at room temperature to perform ion exchange reaction for 24 hours; and then washing with deionized water until the washing liquid has pH of 7, and drying in vacuum to obtain the ion exchange resin catalyst, which is recorded as Cat-DZ-3:
[ example 7 ] catalytic application
The ion exchange resin catalyst prepared in example 1 was used for the transesterification of fats and oils with short-chain alcohols under the following reaction conditions: under the protection of inert gas, the soybean oil and methanol are mixed according to the ratio of 40: 1, then adding a catalyst Cat-A1 with the mass of 5 percent of the mass of the soybean oil, and reacting for 12 hours at the reaction temperature of 60 ℃. After the reaction, a sample was taken and analyzed, and the yield of biodiesel was found to be 95.1% (using the yield of fatty acid methyl ester as an index).
[ examples 8 to 14 ] catalytic applications
The transesterification of fats and oils with short-chain alcohols was carried out by changing the resin catalyst used and the reaction temperature and time, and the other reaction conditions were the same as in example 7, and the reaction results were shown in Table 1.
TABLE 1
[ example 15 ] catalytic application
The catalyst Cat-a1 used in example 7 was filtered, washed, dried, and then used for catalyzing transesterification of fats and oils with short-chain alcohols according to the reaction procedure and reaction conditions of example 7, to obtain results of recycling the catalyst 2 times, as shown in table 2. And analogizing to the above, and respectively carrying out catalytic reactions with the cycle times of 3-5 times, wherein the results are shown in Table 2.
TABLE 2
| Number of cycles | 2 | 3 | 4 | 5 |
| Biodiesel yield/% | 95.1 | 94.9 | 94.8 | 95.0 |
Comparative examples 4 to 6 catalytic applications
The ion exchange resin catalysts prepared in comparative examples 1 to 3 were used for the transesterification of fats and oils with short-chain alcohols. The reaction conditions were as follows: under the protection of inert gas, the soybean oil and methanol are mixed according to the ratio of 40: 1, then adding a comparative catalyst with the mass of 5 percent of the mass of the soybean oil, and reacting at the temperature of 60 ℃ for 12 hours. After the reaction, a sample was taken and analyzed, and the reaction results are shown in Table 3.
TABLE 3
[ COMPARATIVE EXAMPLE 7 ] catalytic applications
The catalyst used in comparative examples 4 to 6 was filtered, washed, dried, and then catalyzed by transesterification of fats and oils with short-chain alcohols according to the reaction steps and reaction conditions of comparative examples 4 to 6, to obtain results of recycling the catalyst 2 times, as shown in table 4. And by analogy, respectively carrying out catalytic reactions with the cycle times of 3-5 times, and the results are shown in Table 4.
TABLE 4
Claims (11)
1. A method for producing biodiesel comprises the steps of contacting grease and short-chain alcohol with an ion exchange resin catalyst under ester exchange reaction conditions; the ion exchange resin catalyst has the following structural general formula:
wherein the content of the first and second substances,
is a gel type nano composite resin matrix;
M-is an anion selected from phosphotungstate, phosphomolybdate, silicotungstate, silicomolybdate, arsenic tungstate, arsenic molybdate, germanium tungstate, germanium molybdate, phosphotungstate, phosphomolybdate vanadate, or phosphomolybdate vanadate;
POSS is a cage-type silsesquioxane unit with the general formula of (-SiO)1.5）m(ii) a m is 6, 8, 10 or 12;
r is a connecting group between the POSS unit and the imidazole cation unit, and R is alkylene;
the gel type nano composite resin matrix is a nano gel type copolymer obtained by in-situ copolymerization of styrene monomers, comonomers and nano materials; the nano material is selected from at least one of multi-wall carbon nano tubes, single-wall carbon nano tubes, C60 or C70 fullerene;
the comonomer is selected from at least one of ethylene glycol dimethacrylate, diacrylene, divinylphenylmethane or divinylbenzene.
2. The method for producing biodiesel according to claim 1, wherein the content of POSS units in the ion exchange resin catalyst is 2 to 8% by weight.
3. The method for producing biodiesel according to claim 1, wherein M is-Is phosphotungstic acid radical ion.
4. The method for producing biodiesel according to claim 1, wherein the alkylene group is selected from the group consisting of methylene, ethylene and propylene.
5. The method for producing biodiesel according to claim 1, wherein the styrenic monomer is at least one selected from styrene, α -methylstyrene or 4-butylstyrene.
6. The method for producing biodiesel according to claim 5, wherein the styrenic monomer is selected from styrene.
7. The biodiesel production process of claim 1, wherein the comonomer is selected from divinylbenzene.
8. The method for producing biodiesel according to claim 1, wherein the nanomaterial is selected from multi-walled carbon nanotubes.
9. The method for producing biodiesel according to claim 1, wherein the styrene monomer is used in an amount of 85 to 95 parts, the comonomer is used in an amount of 2 to 5 parts, and the nanomaterial is used in an amount of 0.1 to 3 parts.
10. The method for producing biodiesel according to claim 1, wherein the fat or oil is selected from any one of animal and vegetable oils of fatty acid glycerides; the short-chain alcohol is selected from any one of methanol, ethanol, propanol or butanol.
11. The method for producing biodiesel according to claim 1, wherein the transesterification reaction conditions include: the molar ratio of the short-chain alcohol to the oil ester is (10-50): 1, the amount of the catalyst is 1-15% of the mass of the raw material grease, the reaction temperature is 40-180 ℃, and the reaction time is 1-24 hours.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102628008A (en) * | 2012-03-27 | 2012-08-08 | 绍兴文理学院 | Method for synthesizing biodiesel from waste grease by catalysis of polymeric ionic liquid |
| CN105772077A (en) * | 2016-03-17 | 2016-07-20 | 中国科学院广州能源研究所 | Magnetic attapulgite supported ionic liquid catalyst and preparation method thereof |
| CN105924464A (en) * | 2016-05-18 | 2016-09-07 | 上海大学 | Octa-imidazolyl POSS room temperature ionic liquid and preparation method thereof |
| 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 |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102628008A (en) * | 2012-03-27 | 2012-08-08 | 绍兴文理学院 | Method for synthesizing biodiesel from waste grease by catalysis of polymeric ionic liquid |
| 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 |
| CN105772077A (en) * | 2016-03-17 | 2016-07-20 | 中国科学院广州能源研究所 | Magnetic attapulgite supported ionic liquid catalyst and preparation method thereof |
| CN105924464A (en) * | 2016-05-18 | 2016-09-07 | 上海大学 | Octa-imidazolyl POSS room temperature ionic liquid and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Multifunctional Mesoporus Ionic Gels and Scaffolds Derived from Polyhedral Oligomeric Silsesquioxanes;Jin Hong Lee, et al.;《ACS Appl.Mater.Interfaces》;20170105;第9卷;第3616-3623页 * |
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