CN101138737A - Molecular sieve type solid alkali catalyst and preparation thereof and application thereof in the preparing of biological diesel oil - Google Patents
Molecular sieve type solid alkali catalyst and preparation thereof and application thereof in the preparing of biological diesel oil Download PDFInfo
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- CN101138737A CN101138737A CNA2007100581758A CN200710058175A CN101138737A CN 101138737 A CN101138737 A CN 101138737A CN A2007100581758 A CNA2007100581758 A CN A2007100581758A CN 200710058175 A CN200710058175 A CN 200710058175A CN 101138737 A CN101138737 A CN 101138737A
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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Abstract
A molecular sieve solid alkali catalyst, preparation of the catalyst and application of the catalyst in the biological diesel oil belong to the biological engineering and energy technical field. The present invention is an alkali metal oxide supported molecular sieve solid alkali catalyst, which uses a MCM-41 meso-pore molecular sieve as a carrier and is properly modified. The alkali metal oxide is Li, Na, K or Rb. The molecular sieve solid alkali catalyst provided by the present invention can be applied as the catalyst in an ester exchange reaction to prepare the biological diesel oil, using the soya beam oil, the rapeseed oil and the wild vegetable oil as the raw material. The present invention overcomes the difficulty of the homogeneous catalyst separation, and reduces a separation course and a water washing course of the prior ester exchange reaction. The modified MCM-41 molecular sieve solid alkali catalyst eliminates the adverse effect of a saponification reaction, promotes the activity and the selectivity of the catalyst, prolongs the usable life and is environment-friendly.
Description
Technical field:
The invention belongs to bioengineering and energy technology field, particularly a kind of molecular sieve type solid alkali catalyst and preparation method thereof, and adopt this catalyst, grease is mixed the method for production biodiesel (fatty acid ester) with short chain alcohol.
Background technology:
With vegetable oil, animal oil, waste edible oil etc. is that raw material and short chain alcohol (methyl alcohol, ethanol etc.) are carried out ester exchange reaction, production biodiesel (fatty acid ester), and byproduct is a glycerine.
The production method of biodiesel adopts chemical method more at present.The core of production of biodiesel is that grease and short chain alcohol are carried out ester exchange reaction under the effect of catalyst, generates corresponding fatty acid ester.
Chemical method is with catalyst such as acid, alkali, and grease and excessive methyl alcohol react the production fatty acid methyl ester at a certain temperature.When adopting homogeneous acid, base catalyst (being generally NaOH, KOH or the concentrated sulfuric acid), product need wash with water, easily causes environmental pollution, and distillation to reclaim the energy consumption of methyl alcohol bigger, glycerine is difficult to separate, and invests bigger etc.When adopting the homogeneous phase alkali as a catalyst, feedstock oil and methyl alcohol must strictly dewater, otherwise saponification takes place easily.And the free acid in the feedstock oil has very big influence to the activity of base catalyst.And liquid acid is corrosive to equipment, therefore equipment is had relatively high expectations.
Summary of the invention:
The objective of the invention is to solve above shortcomings in the prior art, a kind of molecular sieve type solid alkali catalyst is provided, the Preparation of catalysts method, and use this biodiesel, make product not need to wash with water, avoid washing the environmental pollution that brings, reduce the production cost of biodiesel simultaneously.
Molecular sieve type solid alkali catalyst provided by the invention, be to load on alkali-metal alkalescent or neutral compound on the molecular sieve of high-ratio surface as alkaline presoma, handle by temperature-programmed calcination again, make alkali-metal alkalescent or neutral compound at high temperature decompose, obtain thereby produce the highly basic position; Described alkali metal is a kind of among Li, Na, K or the Rb.
Described alkali-metal alkalescent or neutral compound are nitrate or the acetate of Li, Na, K, Rb.
The carrier of this molecular sieve type solid alkali catalyst is the MCM-41 mesopore molecular sieve, and the aperture is even, has higher specific surface area and big adsorption capacity, helps the diffusion of organic molecule.The MCM-41 mesopore molecular sieve can prevent the polycondensation of glycerine.
Described MCM-41 mesopore molecular sieve is the MCM-41 mesopore molecular sieve of the modification after the agent of roasting stripper plate is handled.
Alkali-metal alkalescent or neutral compound are loaded on as alkaline presoma on the MCM-41 of high-ratio surface, can avoid the mesopore molecular sieve structural damage.
A kind of preparation method of above-mentioned molecular sieve type solid alkali catalyst may further comprise the steps:
1) alkali-metal alkalescent or neutral compound are dissolved in the deionized water, add molecular sieve, dipping 10-12h through the agent of roasting stripper plate;
2) with the product of step 1) gained in 100 ℃～150 ℃ dryings;
3) with step 2) products therefrom rises to 500～600 ℃ and keep 5～6h to carry out temperature programming at 500～600 ℃ with the programming rate of 1.5～2 ℃/min from room temperature, molecular sieve type solid alkali catalyst.
Dipping described in the step 1) is an incipient impregnation.
Alkali-metal alkalescent or neutral compound described in the step 1) comprise: the nitrate of Li, Na, K, Rb or acetate, load on it on molecular sieve of high-ratio surface as alkaline presoma, handle by temperature-programmed calcination, make alkali-metal alkalescent or neutral compound at high temperature decompose, thereby can produce the highly basic position, improve the intensity and the distribution of catalyst active center, and can the saboteur structure of sieve.
The mass ratio of molecular sieve type solid alkali catalyst and metal oxide is 100: 2～100: 6.
Molecular sieve type solid alkali catalyst provided by the invention, can be used as with soybean oil, rapeseed oil, wild plant oil is raw material, the Application of Catalyst in the ester exchange reaction of preparation biodiesel.
Advantage of the present invention is:
1. compare with existing homogeneous catalyst production biodiesel, the MCM-41 mesopore molecular sieve of process modification has higher catalytic activity, can make the course of reaction serialization, catalyst easily separates with product, and recyclable regeneration, does not need water-washing process, simplify technological process, reduced manufacturing cost.
2. in Preparation of Catalyst, realize the load of high activity alkalescence component, improved activity of such catalysts, selectivity, increase the service life.
3. the requirement to the reaction temperature of ester exchange reaction reduces, and the requirement of alcohol oil rate reduces, and catalyst amount is less, and can be recycled, and less energy resource consumption reduces the requirement of production equipment.
The specific embodiment:
Embodiment 1:
The first, the preparation of molecular sieve type solid alkali catalyst
The 0.4g lithium nitrate is dissolved in the 12mL deionized water, adds the mesopore molecular sieve MCM-41 of 4g again through the agent of roasting stripper plate.The product of gained is in 100 ℃～150 ℃ oven dry.To dry thing and be raised to 500 ℃ and keep 5h to carry out temperature programming at 500 ℃ with the programming rate of 1.6 ℃/min, molecular sieve type solid alkali catalyst 2wt%Li
2O/MCM-41.
The second, the preparation biodiesel ester exchange reaction in as Application of Catalyst
100g soybean oil and 36g methyl alcohol are put into the 500mL reactor, stir, add the above-mentioned 2wt%Li of 3g
2O/MCM-41 is heated to 130 ℃, reacts after 2 hours, stops to stir and heating.Leave standstill after distilling out excessive methyl alcohol, isolate lower floor's glycerine, promptly obtain the upper strata biodiesel.Product is carried out high performance liquid chromatography-EISD detect, productive rate can reach 73.5% as can be known.
Embodiment 2:
The first, the preparation of molecular sieve type solid alkali catalyst
The 0.38g sodium acetate fully is dissolved in the 12mL deionized water, adds the mesopore molecular sieve MCM-41 of 4g again through the agent of roasting stripper plate.The product of gained is in 100 ℃～150 ℃ oven dry.To dry thing and be raised to 600 ℃ and keep 6h to carry out temperature programming at 600 ℃ with the programming rate of 2 ℃/min, molecular sieve type solid alkali catalyst 3wt%Na
2O/MCM-41.
The second, the preparation biodiesel ester exchange reaction in as Application of Catalyst
100g soybean oil and 36g methyl alcohol are put into the 500mL reactor, stir, add the above-mentioned 3wt%Na of 3g
2O/MCM-41 is heated to 130 ℃, reacts after 2 hours, stops to stir and heating.Leave standstill after distilling out excessive methyl alcohol, isolate lower floor's glycerine, promptly obtain the upper strata biodiesel.Product is carried out high performance liquid chromatography-EISD detect, productive rate can reach 90.0% as can be known.
Embodiment 3:
The first, the preparation of molecular sieve type solid alkali catalyst
0.4g potassium nitrate fully is dissolved in the 12mL deionized water, adds the mesopore molecular sieve MCM-41 of 4g again through the agent of roasting stripper plate.The product of gained is in 100 ℃～120 ℃ oven dry.To dry thing and be raised to 500 ℃ and keep 5h to carry out temperature programming at 500 ℃ with the programming rate of 1.6 ℃/min, molecular sieve type solid alkali catalyst 4wt%K
2O/MCM-41.
The second, the preparation biodiesel ester exchange reaction in as Application of Catalyst
100g soybean oil and 36g methyl alcohol are put into the 500mL reactor, stir, add the above-mentioned 4wt%K of 3g
2O/MCM-41 is heated to 130 ℃, reacts after 2 hours, stops to stir and heating.Leave standstill after distilling out excessive methyl alcohol, isolate lower floor's glycerine, promptly obtain the upper strata biodiesel.Product is carried out high performance liquid chromatography-EISD detect, productive rate can reach 89.8% as can be known.
Embodiment 4:
The first, the preparation of molecular sieve type solid alkali catalyst
The 0.4g rubidium nitrate fully is dissolved in the 12mL deionized water, adds the mesopore molecular sieve MCM-41 of 4g again through the agent of roasting stripper plate.The product of gained is in 100 ℃～120 ℃ oven dry.To dry thing and be raised to 500 ℃ and keep 5h to carry out temperature programming at 500 ℃ with the programming rate of 1.6 ℃/min, molecular sieve type solid alkali catalyst 6wt%Rb
2O/MCM-41.
The second, the preparation biodiesel ester exchange reaction in as Application of Catalyst
100g soybean oil and 36g methyl alcohol are put into the 500mL reactor, stir, add the above-mentioned 6wt%Rb of 3g
2O/MCM-41 is heated to 130 ℃, reacts after 2 hours, stops to stir and heating.Leave standstill after distilling out excessive methyl alcohol, isolate lower floor's glycerine, promptly obtain the upper strata biodiesel.Product is carried out high performance liquid chromatography-EISD detect, productive rate can reach 64.3% as can be known.
Claims (10)
1. molecular sieve type solid alkali catalyst, it is characterized in that: this catalyst is to load on alkali-metal alkalescent or neutral compound on the molecular sieve of high-ratio surface as alkaline presoma, handle by temperature-programmed calcination again, make alkali-metal alkalescent or neutral compound at high temperature decompose, obtain thereby produce the highly basic position; Described alkali metal is a kind of among Li, Na, K or the Rb.
2. molecular sieve type solid alkali catalyst according to claim 1, it is characterized in that: the molecular sieve of described high-ratio surface is the MCM-41 mesopore molecular sieve, and the aperture is even, between 1.5nm～10nm, have higher specific surface area 1000m/g and big adsorption capacity 0.7mg/L; Described alkali-metal alkalescent or neutral compound are alkali metal oxide.
3. molecular sieve type solid alkali catalyst according to claim 2 is characterized in that: described MCM-41 mesopore molecular sieve is the MCM-41 mesopore molecular sieve of the modification after the agent of roasting stripper plate is handled.
4. the preparation method of the described molecular sieve type solid alkali catalyst of claim 1 is characterized in that, this method may further comprise the steps:
1) alkali-metal alkalescent or neutral compound are dissolved in the deionized water, add molecular sieve, dipping 10-12h through the agent of roasting stripper plate;
2) with the product of step 1) gained in 100 ℃～150 ℃ dryings;
3) with step 2) products therefrom rises to 500～600 ℃ and keep 5～6h to carry out temperature programming at 500～600 ℃ with the programming rate of 1.5～2 ℃/min from room temperature, molecular sieve type solid alkali catalyst.
5. preparation method according to claim 4, the mass ratio that it is characterized in that molecular sieve type solid alkali catalyst and metal oxide is 100: 2～100: 6.
6. preparation method according to claim 4, it is characterized in that described alkali-metal alkalescent or neutral compound comprise: the nitrate of Li, Na, K, Rb or acetate, load on it on molecular sieve of high-ratio surface as alkaline presoma, handle by temperature-programmed calcination, make alkali-metal alkalescent or neutral compound at high temperature decompose, thereby produce the highly basic position, improve the intensity and the distribution of catalyst active center, and structure that can saboteur's sieve.
7. preparation method according to claim 4 is characterized in that described molecular sieve is MCM-41.
8. preparation method according to claim 7 is characterized in that carrier is the MCM-41 mesopore molecular sieve, and the aperture is even, between 1.5nm～10nm, has higher specific surface area and big adsorption capacity, helps the diffusion of organic molecule.
9. preparation method according to claim 4 is characterized in that the dipping described in the step 1) is an incipient impregnation.
10. the described molecular sieve type solid alkali catalyst of claim 1, as being raw material with soybean oil, rapeseed oil, wild plant oil, the Application of Catalyst in the ester exchange reaction of preparation biodiesel.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2007100581758A CN101138737A (en) | 2007-07-18 | 2007-07-18 | Molecular sieve type solid alkali catalyst and preparation thereof and application thereof in the preparing of biological diesel oil |
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| CNA2007100581758A CN101138737A (en) | 2007-07-18 | 2007-07-18 | Molecular sieve type solid alkali catalyst and preparation thereof and application thereof in the preparing of biological diesel oil |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010792A (en) * | 2010-12-15 | 2011-04-13 | 东南大学 | Continuous production method of biodiesel |
| CN102698811A (en) * | 2012-05-18 | 2012-10-03 | 南京工业大学 | Solid basic catalyst, preparation method of solid basic catalyst and application of solid basic catalyst in ester exchange reaction |
| CN103191768A (en) * | 2013-03-22 | 2013-07-10 | 南京工业大学 | Mesoporous solid strong-alkaline catalyst and preparation method and application of catalyst |
| CN106807436A (en) * | 2017-01-25 | 2017-06-09 | 东南大学 | A kind of preparation method of the acid base catalysators of microwave modification Ca Zr/H ZSM 5 |
| CN116139911A (en) * | 2023-04-20 | 2023-05-23 | 山东鲁控电力设备有限公司 | Application of mesoporous molecular sieve-based solid acid-base catalyst in synthesis of transformer insulating oil |
-
2007
- 2007-07-18 CN CNA2007100581758A patent/CN101138737A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010792A (en) * | 2010-12-15 | 2011-04-13 | 东南大学 | Continuous production method of biodiesel |
| CN102010792B (en) * | 2010-12-15 | 2012-08-22 | 东南大学 | Continuous production method of biodiesel |
| CN102698811A (en) * | 2012-05-18 | 2012-10-03 | 南京工业大学 | Solid basic catalyst, preparation method of solid basic catalyst and application of solid basic catalyst in ester exchange reaction |
| CN103191768A (en) * | 2013-03-22 | 2013-07-10 | 南京工业大学 | Mesoporous solid strong-alkaline catalyst and preparation method and application of catalyst |
| CN106807436A (en) * | 2017-01-25 | 2017-06-09 | 东南大学 | A kind of preparation method of the acid base catalysators of microwave modification Ca Zr/H ZSM 5 |
| CN106807436B (en) * | 2017-01-25 | 2019-04-09 | 东南大学 | A kind of preparation method of microwave modification Ca-Zr/H-ZSM-5 acid base catalysator |
| CN116139911A (en) * | 2023-04-20 | 2023-05-23 | 山东鲁控电力设备有限公司 | Application of mesoporous molecular sieve-based solid acid-base catalyst in synthesis of transformer insulating oil |
| CN116139911B (en) * | 2023-04-20 | 2023-06-30 | 山东鲁控电力设备有限公司 | Application of mesoporous molecular sieve-based solid acid-base catalyst in synthesis of transformer insulating oil |
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