CN101875723A - Resin and preparation method thereof, and catalyst used for preparing biodiesel and preparation method thereof - Google Patents
Resin and preparation method thereof, and catalyst used for preparing biodiesel and preparation method thereof Download PDFInfo
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- CN101875723A CN101875723A CN2009101071732A CN200910107173A CN101875723A CN 101875723 A CN101875723 A CN 101875723A CN 2009101071732 A CN2009101071732 A CN 2009101071732A CN 200910107173 A CN200910107173 A CN 200910107173A CN 101875723 A CN101875723 A CN 101875723A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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Abstract
The invention discloses a resin and a preparation method thereof. The resin consists of repeat units in the following formula, wherein R is one of -CH3, -CH2CH3, -CH(CH3)2, -C(CH3)3, -OCH3 and -OH; the inherent viscosity of the resin is 0.3-0.4dL/g; and the R group is a donor group. The invention also discloses a catalyst used for preparing biodiesel and a preparation method thereof. The catalyst comprises the resin and a carrier used for supporting the resin. Compared with the prior art, the resin has low crystallinity and then has high solubility property in an organic solvent; meanwhile, the catalyst has low processing difficulty in the process of grinding into powder.
Description
Technical field
The present invention relates to a kind of resin and preparation method thereof, and a kind of Catalysts and its preparation method that is used to prepare biofuel.
Background technology
Along with rapid economy development, the demand for energy in the whole world increases day by day; Biofuel has great potential and vast market prospect as the cleaning liq biofuel of alternative petrifaction diesel.
What present industrial production biofuel adopted is transesterification or transesterification reaction, promptly under acidity or basic catalyst and hot conditions, carry out transesterification reaction with animal grease or Vegetable oil lipoprotein and low-carbon alcohol such as methyl alcohol or ethanol, generate corresponding fatty acid methyl ester or fatty-acid ethyl ester, promptly get biofuel.Catalyst for ester exchange reaction comprises basic catalyst, an acidic catalyst, amberlite ester catalyst etc.
Ion-exchange resin is an important branch of solid catalyst research direction.With solid alkali anionite-exchange resin is that catalyzer carries out greasy transesterification reaction, has the easily separated recovery of catalyzer, can reuse, not pollute advantages such as finished product and reaction conditions gentleness.Xie Wenlei has carried out the research that stearic exchanges with 717 pretreated type anionite-exchange resin of NaOH solution as catalyzer in " the greasy transesterify of strong anion-exchange resin heterogeneous catalyst " (applied chemistry, October calendar year 2001) in the literary composition.Xie Wenlei with soybean oil and leaf fat with 6: 4 abundant mixings as raw material, add the catalyzer that accounts for oil quality 10%, under 50 ℃, reaction 2.5h, the transesterify degree is big, transformation efficiency is high.
Qin Shirong, " the anionic resin catalysis prepares the research of biofuel ", Master's thesis, in June, 2008, the quaternary line style strong base resin that extraordinary polyethersulfone type resins goes out and the blend of silicon-dioxide and quaternary line style strong base resin that general polyethersulfone type resins goes out and the blend of silicon-dioxide are heterogeneous catalyst, catalysis the transesterification reaction of soybean oil and methyl alcohol, prepare fatty acid methyl ester.The a series of fatty acid methyl ester admixture that synthesizes can be determined by the test of gas-chromatography and mass spectrometry.The catalytic efficiency that aforesaid method has the catalyzer for preparing is largely increased, but because resin degree of crystallinity is higher, causes resin dissolves difficulty in the chloromethylation process; Resin degree of crystallinity height causes not easy grinding of catalyst fines simultaneously.
Summary of the invention
The problem to be solved in the present invention is to reduce resin crystallinity with respect to prior art, and then has improved the solubility property of resin in organic solvent, has reduced the difficulty of processing of catalyzer in the grind into powder process simultaneously.
The invention provides a kind of resin, described resin is made of the repeating unit of following formula: wherein, R is-CH
3,-CH
2CH
3,-CH (CH
3)
2,-C (CH
3)
3,-OCH
3A kind of among the ,-OH, the limiting viscosity of resin is 0.3-0.4dL/g, and the R base is electron-donating group,
The preparation method of above-mentioned resin, 1) will contain the polysulfones of side-chain radical, be dissolved in the solvent, add chloromethylation reagent and the initiation reaction of Lewis alkaline catalysts, obtain containing the chloromethyl polysulphone of side-chain radical after the reaction; 2) chloromethyl polysulphone that will contain side-chain radical places trimethylamine solution, is positioned in the alkaline aqueous solution and soaks, and filters, washing is to neutral, obtains resin.
A kind of catalyzer that is used to prepare biofuel, resin and the carrier that is used for the described resin of load that described catalyzer is above-mentioned.
A kind of Preparation of catalysts method, (1) will contain the polysulfones of side-chain radical, be dissolved in the solvent, add chloromethylation reagent and the initiation reaction of Lewis alkaline catalysts, obtain containing the chloromethyl polysulphone of side-chain radical after the reaction; (2) chloromethyl polysulphone that will contain side-chain radical is dissolved in the solvent, with the carrier blend, oven dry, grinds, and has obtained containing the blended powder of the chloromethyl polysulphone and the carrier of side-chain radical; (3) will contain the chloromethyl polysulphone of side-chain radical and the blended powder of carrier and place Trimethylamine 99 to soak, and be positioned in the alkaline aqueous solution again and soak, and filter, wash, obtain catalyzer to neutral.
Adopt resin of the present invention, because the introducing of side chain, the polysulfones that has side-chain radical that the present invention is obtained is soluble in the organic solvent, thereby helps the carrying out of chloromethylation; And the resin degree of crystallinity for preparing reduces greatly, makes the easier grinding of blend of resin and carrier, thereby Preparation of catalysts is more prone to.
Embodiment
The invention provides a kind of resin, described resin is made of the repeating unit of following formula: wherein, R is-CH
3,-CH
2CH
3,-CH (CH
3)
2,-C (CH
3)
3,-OCH
3A kind of among the ,-OH, the limiting viscosity of resin is 0.3-0.4dL/g, and the R base is electron-donating group,
The molecular weight of R base is big more, and the crystal property of resin is poor more, and solubility property is good more, thereby solubility property is: the tertiary butyl＞sec.-propyl＞ethyl＞methyl; The R base must be an electron-donating group simultaneously, and electron withdrawing group is unfavorable for the carrying out of chloromethylation.
The polysulfones that will contain side-chain radical is the known a kind of compound of those skilled in the art, and is commercially available.
Polysulfones has another name called, dihydroxyphenyl propane-4, and the 4`-sulfobenzide, for the known a kind of resin of those skilled in the art, by dihydroxyphenyl propane sodium salt (or sylvite) and 4,4 '-dichloro diphenyl sulfone polycondensation and making, commercially available, the structural formula of concrete repeating unit is as follows:
The preparation method of above-mentioned resin, 1) will contain the polysulfones of side-chain radical, be dissolved in the solvent, add chloromethylation reagent and the initiation reaction of Lewis alkaline catalysts, obtain containing the chloromethyl polysulphone of side-chain radical after the reaction; 2) chloromethyl polysulphone that will contain side-chain radical places trimethylamine solution, is positioned in the alkaline aqueous solution and soaks, and filters, washing is to neutral, obtains resin.
Described chloromethylation reagent and Lewis alkaline catalysts, the temperature of reaction of the chloromethylation of initiation are known temperature of reaction of those skilled in the art and reaction times, and described temperature of reaction is generally 0-25 ℃, and the reaction times is 0.5-4h.
Soaking in Trimethylamine 99 is in order to carry out quaterisation.Soaking in alkaline aqueous solution is to carry out-the OH replacement(metathesis)reaction.Quaterisation and-OH displacement is that the condition of alkali replacement(metathesis)reaction is known temperature of reaction of those skilled in the art and reaction times, for example, is that the time that Trimethylamine 99 soaks is 8-20h, temperature is 25-40 ℃; The NaOH alkali metathetical time is 8-20h, and temperature is 25-40 ℃.
Described adding chloromethylation reagent and the initiation reaction of Lewis alkaline catalysts, obtain containing the chloromethyl polysulphone of side-chain radical after the reaction, for the known utilization of those skilled in the art contains separating out that the difference of the solubleness of chloromethyl polysulphone in different solvents of side-chain radical causes, for example, the present invention adds entry or ethanol in reacted macromolecular solution, solvent chloroform by water or ethanol infinite dilution after, the solubleness of chloromethyl polysulphone in water or ethanol that contains side chain is far smaller than chloroform, is therefore separated out from the chloromethyl polysulphone that contains side-chain radical.
A kind of catalyzer that is used to prepare biofuel, resin and the carrier that is used for the described resin of load that described catalyzer is above-mentioned.Only be that resin can not use as the catalyzer of biofuel, because resin is the compactness material, the specific surface machine is very little, therefore needs the big material of specific surface area such as silicon-dioxide as carrier, could embody catalytic activity in actual applications like this.
Described carrier has played loaded resin, the effect of dispersion resin.Too for a short time, just do not have an effect of load dispersive when what the amount of described carrier accounted for catalyzer, therefore, preferably, in the total amount of resin and carrier, described carrier accounts for the 50-90% quality of resin and carrier total amount.
Described carrier is SiO 2 powder or titania powder.Described carrier can be commercially available SiO 2 powder or titania powder, and for example particle diameter is a 50-200 purpose SiO 2 powder.
A kind of Preparation of catalysts method, (1) will contain the polysulfones of side-chain radical, be dissolved in the solvent, add chloromethylation reagent and the initiation reaction of Lewis alkaline catalysts, and the extraction of reaction back obtains containing the chloromethyl polysulphone of side-chain radical; (2) chloromethyl polysulphone that will contain side-chain radical is dissolved in the solvent, with the carrier blend, oven dry, grinds, and has obtained containing the blended powder of the chloromethyl polysulphone and the carrier of side-chain radical; (3) will contain the chloromethyl polysulphone of side-chain radical and the blended powder of carrier and place Trimethylamine 99 to soak, and be positioned in the alkaline aqueous solution again and soak, and filter, wash, obtain catalyzer to neutral.
Described alkaline aqueous solution is a kind of in sodium hydroxide, the potassium hydroxide aqueous solution.
The molecular formula of described chloromethylation reagent is ClCH
2O (CH
2)
mCH
3, described m is 4-12.Chloromethylation reagent is toxicant, and carbochain is long more, and then the volatility of chloromethylation reagent is poor more, and the environmental pollution that causes is also just low more.Therefore the preferred m value of the present invention is more than or equal to 4, smaller or equal to 12.
Described Lewis alkaline catalysts is the known Lewis alkaline catalysts of those skilled in the art, for example, and a kind of in zinc chloride, tin chloride, the aluminum chloride.
Described solvent is the known solvent of those skilled in the art, as chloroform.
Concrete reaction process is shown in following equation formula 1:
Formula 1
Be described further below by embodiment:
Embodiment 1
The polysulfones that the 5g side chain is contained the tertiary butyl is dissolved in the 50ml solvent chloroform, under the ice-water bath condition, add 30ml as the chloromethyl butyl ether of chloromethylation reagent and the Lewis alkaline catalysts tin chloride of 6ml, reaction 2h, product is separated out in water, washing, 60 ℃ of down oven dry have obtained the polysulfones that the chloromethylation side chain contains the tertiary butyl.The polysulfones that this chloromethylation side chain is contained the tertiary butyl places 100% trimethylamine solution, under 40 ℃, soaks and puts 12h, filter, filter cake is placed the NaOH solution of 1mol/L, under 40 ℃, soak and put 12h, obtain resin and be washed to neutrality, 60 ℃ of oven dry down obtain Resin A of the present invention.
Embodiment 2
It is the blend of 50-200 purpose SiO 2 powder that the polysulfones that the chloromethylation side chain that embodiment 1 prepares contains the tertiary butyl is put into the particle size range that adds 35g before the trimethylamine solution, 50 ℃ of oven dry, grind into powder.Ground powder is placed the trimethylamine solution of embodiment 1, and other is identical with embodiment 1, obtains powder catalyst B.
Embodiment 3
The polysulfones that the 5g side chain is contained sec.-propyl is dissolved in the 40ml solvent chloroform, add 40ml down as the chloromethyl hexyl ether of chloromethylation reagent and the Lewis alkaline catalysts zinc chloride of 9g at 25 ℃, reaction 3h, product is separated out in aqueous ethanolic solution, washing, dry down, obtain the chloromethylation products of this resin for 50 ℃.This product is dissolved in chloroform, and the particle size range that adds 35g is the blend of 50-200 purpose SiO 2 powder, 50 ℃ of oven dry, grind into powder.Ground powder is placed 50% trimethylamine solution, under 40 ℃, soaks and put 20h, filter, filter cake is placed the NaOH solution of 2mol/L, under 40 ℃, soak and put 8h, again with the powder washing to neutral, 60 ℃ of oven dry down obtain powder catalyst C.
Embodiment 4
The polysulfones that the 5g side chain is contained methyl is dissolved in the 45ml solvent chloroform, under the ice-water bath condition, add 30ml as the chloromethyl butyl ether of chloromethylation reagent and the Lewis alkaline catalysts tin chloride of 6ml, reaction 4h, product is separated out in water, washing, dry down, obtain the chloromethylation products of this resin for 50 ℃.This product is dissolved in chloroform, adds the 70-100 purpose SiO 2 powder of 40g, 50 ℃ of steamings remove chloroform, grind into powder.Ground powder is placed 70% trimethylamine solution, under 25 ℃, soaks and put 15h, filter, filter cake is placed the NaOH solution of 1mol/L, under 25 ℃, soak and put 15h, again with the powder washing to neutral, 60 ℃ of oven dry down obtain powder catalyst D.
Comparative Examples 1
With embodiment 2, difference is that described reaction raw materials is changed to polysulfones by the polysulfones that side chain contains the tertiary butyl.Prepare powder catalyst E.
Testing method:
1, tests about resin
All resins of the present invention can detect by the known hydrogen spectrum nucleus magnetic resonance of those skilled in the art (H-NMR), and solvent adopts (this CDCl
3Be deuterochloroform (CDCl
3).Resin of the present invention occurs one and splits not of uniform size bimodal of branch at δ 4.5 places, the peak at δ 4.5 places is-CH
2The charateristic avsorption band of H among the Cl illustrates that the resin that the present invention prepares is the resin that contains side-chain radical of chloromethylation.
2, test about the catalytic effect of catalyzer
The preparation method of described biofuel is the known general knowledge of those skilled in the art.The raw material of reaction be the low acid number vegetables oil (acid number is less than 10mg/L KOH) of soybean oil, peanut wet goods and low-carbon alcohol such as methyl alcohol, ethanol (because of, the carbon chain length of low-carbon alcohol sterically hindered long), the two is joined in the there-necked flask, add a certain amount of catalyzer again.Temperature of reaction is 45-75 ℃, and the reaction times is 2-12h, and high-speed stirring, the mass percent of catalyzer and stock oil are 10-50%, and the oleyl alcohol volume ratio is 1: 1-1: 6.Post catalyst reaction adopts filtering separation, and low-carbon alcohol adopts air distillation, and the byproduct of reaction glycerol adopts the mode of centrifugation.Catalyzer after the use can use repeatedly through the reaction of living again.
Glycerol is to certainly exist by product in the fatty acid ester of low-carbon alcohol preparation process, adopts the mode of centrifugation just can remove, and the preparation feedback equation formula of following biofuel 2 is an example with methyl alcohol:
Formula 2
R1 in the formula 2, R2, R3 are the saturated and undersaturated alkyl of carbonatoms 17-21, be used to represent that different greases is exactly a kind of mixture such as soybean oil and peanut oil itself, no definite molecular formula, reacted product is the series mixture of fatty acid methyl ester or the series mixture of fatty-acid ethyl ester, and these starting material by reaction are that low-carbon alcohol decides.
Add 3g catalyst B, C, D, E respectively in the mixing solutions of 4 parts of soybean oil 8ml and methyl alcohol 24ml, temperature of reaction is 60 ℃, and the reaction times is 8h, high-speed stirring.Post catalyst reaction adopts filtering separation, and methyl alcohol adopts air distillation, and glycerol adopts the mode of centrifugation.The mixture that reaction obtains fatty acid methyl ester is biofuel B1, C1, D1, E1, and test obtains reaction conversion ratio and is respectively 95%, 92%, 90%, 85%.
Transformation efficiency at B1, C1, D1, E1 employing gas Chromatographic Determination catalyst transesterification reaction adopts following formula to calculate this reaction conversion ratio.
X% is a reaction conversion ratio;
A is the area total amount of fatty acid methyl ester in gas-chromatography of catalyst preparation of the present invention;
B is BF
3The area total amount of fatty acid methyl ester in gas-chromatography with the NaOH catalytic preparation; And BF
3With the catalytic efficiency 100% of the fatty acid methyl ester of NaOH catalytic preparation be the common practise of this area.
3, the regeneration of the catalyzer after the use
Catalyzer after the use can adopt the renovation process of the known catalyzer of those skilled in the art to regenerate.
Used catalyzer is put in the citric acid solution of 5wt%, stirred 30min, after the filtration, soak the NaOH solution 12h that places 1mol/L, keep 40 ℃, powder catalyst is filtered, be washed to neutrality.Catalyzer after the regeneration is reused, and the transformation efficiency that obtains fatty acid methyl ester is more than 90%.Wherein, the washing of citric acid is in order to remove the grease of used catalyst surface.
Adopt resin of the present invention, because the introducing of side chain, the polysulfones that has side-chain radical that the present invention is obtained is soluble in the organic solvent, thereby helps the carrying out of chloromethylation; And the resin degree of crystallinity for preparing reduces greatly, makes the easier grinding of blend of resin and carrier, thereby Preparation of catalysts is more prone to.The catalytic efficiency of the catalyzer that the present invention simultaneously prepares increases than prior art.
Claims (13)
1. resin, described resin is made of the repeating unit of following formula: wherein, R is-CH
3,-CH
2CH
3,-CH (CH
3)
2,-C (CH
3)
3,-OCH
3A kind of among the ,-OH, the limiting viscosity of resin is 0.3-0.4dL/g, and the R base is electron-donating group,
2. the preparation method of the described resin of claim 1,1) will contain the polysulfones of side-chain radical, be dissolved in the solvent, add chloromethylation reagent and the initiation reaction of Lewis alkaline catalysts, obtain containing the chloromethyl polysulphone of side-chain radical after the reaction; 2) chloromethyl polysulphone that will contain side-chain radical places trimethylamine solution, is positioned in the alkaline aqueous solution and soaks, and filters, washing is to neutral, obtains resin.
3. preparation method according to claim 2, the structural formula of described chloromethylation reagent is ClCH
2O (CH
2)
mCH
3, described m is 4-12.
4. preparation method according to claim 2, described Lewis alkaline catalysts is a kind of in zinc chloride, tin chloride, the aluminum chloride.
5. preparation method according to claim 2, described solvent is a chloroform.
6. catalyzer that is used to prepare biofuel, described catalyzer comprise the described resin of claim 1 and are used for the carrier of the described resin of load.
7. catalyzer according to claim 6, in the total amount of resin and carrier, described carrier accounts for 50 quality %-90 quality % of resin and carrier total amount.
8. according to claim 6 or 7 described catalyzer, described carrier is SiO 2 powder or titania powder.
9. described Preparation of catalysts method of claim 6, (1) will contain the polysulfones of side-chain radical, be dissolved in the solvent, add chloromethylation reagent and the initiation reaction of Lewis alkaline catalysts, obtain containing the chloromethyl polysulphone of side-chain radical after the reaction; (2) chloromethyl polysulphone that will contain side-chain radical is dissolved in the solvent, with the carrier blend, oven dry, grinds, and has obtained containing the blended powder of the chloromethyl polysulphone and the carrier of side-chain radical; (3) will contain the chloromethyl polysulphone of side-chain radical and the blended powder of carrier and place Trimethylamine 99 to soak, and be positioned in the alkaline aqueous solution again and soak, and filter, wash, obtain catalyzer to neutral.
10. Preparation of catalysts method according to claim 9, described alkaline aqueous solution are a kind of in sodium hydroxide, the potassium hydroxide aqueous solution.
11. preparation method according to claim 9, described carrier is SiO 2 powder or titania powder.
12. preparation method according to claim 9, the structural formula of described chloromethylation reagent is ClCH
2O (CH
2)
mCH
3, described m is 4-12.
13. preparation method according to claim 9, described Lewis alkaline catalysts is a kind of in zinc chloride, tin chloride, the aluminum chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101071732A CN101875723B (en) | 2009-04-30 | 2009-04-30 | Resin and preparation method thereof, and catalyst used for preparing biodiesel and preparation method thereof |
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|---|---|---|---|
| CN2009101071732A CN101875723B (en) | 2009-04-30 | 2009-04-30 | Resin and preparation method thereof, and catalyst used for preparing biodiesel and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN101875723A true CN101875723A (en) | 2010-11-03 |
| CN101875723B CN101875723B (en) | 2012-06-20 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110194838A (en) * | 2019-05-28 | 2019-09-03 | 上海大学 | 1- pyrenyl is functionalized polysulfone material and preparation method thereof |
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|---|---|---|---|---|
| CN1059449C (en) * | 1996-07-08 | 2000-12-13 | 中国科学院生态环境研究中心 | Preparation method for high-viscosity chloromethyl polysulphone |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110194838A (en) * | 2019-05-28 | 2019-09-03 | 上海大学 | 1- pyrenyl is functionalized polysulfone material and preparation method thereof |
| CN110194838B (en) * | 2019-05-28 | 2021-07-06 | 上海大学 | 1-pyrenyl functionalized polysulfone material and preparation method thereof |
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