CN104525241B - Solid alkali catalyst as well as preparation method and application thereof in glycerinum alcoholysis reaction - Google Patents
Solid alkali catalyst as well as preparation method and application thereof in glycerinum alcoholysis reaction Download PDFInfo
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- CN104525241B CN104525241B CN201410786676.8A CN201410786676A CN104525241B CN 104525241 B CN104525241 B CN 104525241B CN 201410786676 A CN201410786676 A CN 201410786676A CN 104525241 B CN104525241 B CN 104525241B
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Abstract
The invention belongs to the technical field of chemical engineering and energy, and in particular discloses a solid alkali catalyst as well as a preparation method and application thereof in glycerinum alcoholysis reaction. The catalyst is a mesoporous material loaded alkaline earth metal oxide catalyst which comprises active ingredient alkaline earth metal selected from one or more of oxides including MgO, CaO and SrO; the capacity of the alkaline earth metal accounts for 4% to 20% of the mass of a mesoporous material. The catalyst is environment-friendly, simple and efficient in preparation method, relatively large in specific surface area, aperture and strong basicity; and when used in glycerinum alcoholysis reaction, the catalyst is small in loss, high in catalysis activity and can be recycled.
Description
Technical field
The invention belongs to chemical and energy technology field, and in particular to a kind of solid base catalyst and its synthesis side
Method, and the application in glycerolysis reaction.
Background technology
Energy crisis and environmental pollution are the common issues of current human society concern, develop a kind of replacing for green non-pollution
It is study hotspot nearly ten years for the energy.Biodiesel is typical " green energy resource ", has worldwide been obtained extensively
Research with application.At present, it is production cost to restrict one of bottleneck of biodiesel development.The application valency of exploitation by-product glycerin
Value advantageously accounts for the production of biodiesel and application problem.
The reaction of glycerolysis vegetable oil is one of important method of glycerine application, its glycerol production monoesters and diglyceride and
Its mixture list double glyceride is a kind of important emulsifying agent, is had in fields such as food, medicine, cosmetics, health care, chemical syntheses
And be widely applied.Glycerolysis is reacted typically under 200-260 DEG C of hot conditions, using homogeneous base catalysis glycerolysis glycerine
Three esters（The main component of vegetable oil, animal fat）, conventional catalyst has NaOH, KOH, Ca (OH)2Deng product is after alcoholysis
The mixture of monoglyceride, diglyceride, unreacted glycerine and grease, through being fractionated purification highly purified glycerine list is obtained
Ester, diglyceride.Wherein, Ca (OH)2The color and luster of catalysate more meets the requirement of food industry.However, using homogeneous catalysis
Agent corrosive equipment, catalyst is difficult to separate recycling, and accessory substance generation is had in last handling process.Thus, solid base is urged
Agent is reusable due to being easily isolated, and becomes most one of environment-friendly catalyst of potential in research.
Chinese patent CN 1585814A disclose a kind of chemical method for preparing 1,3- triglyceride oils.The method uses one
The alkali metal salt or alkali salt of first carboxylic acid or dicarboxylic acids to drive certain condition under glycerolysis, so as to prepare business
Industry, food-grade 1,3- triglyceride oils.Chinese patent CN 102191134A disclose a kind of partial glyceride（It is single double sweet
Grease）Preparation method, one or more the mixture through catalytic using potassium hydroxide, NaOH or calcium hydroxide is sweet
Oily alcoholysis reaction, obtains partial glycerol mixture.A. Corma etc. has investigated Cs-MCM-41, Cs-Sepiolite, MgO and
Application of the MgAl hydrotalcites in glycerolysis soya-bean oil, it is found that MgO and low aluminum hydrotalcite show preferable monoglyceride yield
(Corma, A. et al., Catalysts for the production of fine chemicals-Production
of food emulsifiers, monoglycerides, by glycerolysis of fats with solid base
catalysts, Journal of Catalysis, 1998. 173(2):315-321).Volodymyr Brei etc. use solid
Fixed bed reactor, have studied MgO-TiO2, MgO-La2O3, MgO-ZrO, hydrotalcite, ZnO-Al2O3, ZnO-MgO, CaO-
Application of the catalyst such as ZnO in glycerolysis soya-bean oil, wherein, CaO-ZnO and hydrotalcite all show higher activity
(Brei, V., et al., Study of a continuous process of glycerolysis of rapeseed
oil with the solid base catalysts, Chemistry & Chemical Technology, 2012, 6
(1): 89-94)。
In catalyst disclosed above, the activity and stability of catalyst become restriction solid base catalyst industrially
Large-scale application main cause.
The content of the invention
It is an object of the invention to provide a kind of solid base catalyst and its system with efficient catalysis activity and stability
Preparation Method, and the reaction of glycerolysis vegetable oil is applied to, its preparation process is simple, and catalyst loss in the solution is little.
Solid base catalyst proposed by the present invention, be mesoporous material load alkaline-earth metal catalyst, active component alkaline earth
Metal for oxide M gO, CaO, SrO one kind, or wherein several mixture；The load capacity of alkaline-earth metal is mesoporous material
Between 4% to the 20% of quality.
The present invention also provides the synthetic method of above-mentioned support type alkaline-earth metal catalyst, specifically using step impregnation method, its
Step is as follows：
（1）According to the amount of mesoporous material supported alkaline earth metal, alkali salt, mesoporous material and solvent are weighed, mixing is ground
It is milled to form paste mixture；
（2）Then paste mixture is added in solvent, is stirred, flowed back at boiling temperature overnight；
（3）Jing is filtered, and obtains white solid, is dried, then the roasting 5- under the conditions of 450-600 DEG C, air atmosphere
8 hours.
In the present invention, described alkali salt is Mg (NO3)2、Ca(NO3)2、Sr(NO3)2、Ca(CH3COO)2、Ca
(OH)2、Mg(CH3COO)2Or Sr (CH3COO)2In one kind, or wherein several mixture.
In the present invention, described mesoporous material can be the one kind in SBA-15, SBA-16, KIT-6, or wherein several
Mixture.
In the present invention, described solvent is water or n-hexane.
Load type solid body base catalyst using the present invention is as follows in the method that glycerolysis vegetable oil reacts：
Before reaction, by catalyst, at the reaction temperatures glycerine processes 25-40 min；Vegetable oil is added to into glycerin catalytic agent
In mixed liquor；Under 180-240 DEG C of reaction temperature, the mixing speed of 300-1000 rpm, 1-24 hours are reacted, that is, be obtained
Product.
Heretofore described vegetable oil can be the vegetable oil such as soya-bean oil, corn oil, palm oil, cottonseed oil, olive oil
One or more mixture.
In the present invention, the usage amount of catalyst is the 3%-10% of plant oil quality.
In the present invention, glycerine is 2 with the mol ratio of vegetable oil:1-10:1.
The preparation method of the load type solid body base catalyst of the present invention is simple, has Large ratio surface and orderly hole using carrier
Road, obtained catalyst solubility in glycerine is very low, greatly reduces the loss of active component.It is applied to glycerolysis plant
In oil reaction, vegetable oil conversion ratio can be to 100%.Solid base catalyst can adopt the method for filtering or being centrifuged to separate, can be again
It is multiple to utilize；Product is monoglyceride and diglyceride, i.e. list double glyceride.Single double glyceride can be used as in itself a kind of emulsification
Agent.Meanwhile, the separation of monoglyceride and diglyceride is more easy compared to the separation of diglyceride and triglycerides.
Specific embodiment
The invention is further illustrated by the following examples.
Embodiment 1
By 2 grams of SBA-16,2.3 grams of Ca (NO3)2 .4H2O and 10 milliliter of water mixing, grinding is uniform；30 milliliters of water are added,
Night is flow through next time at 100 DEG C；The mixed liquor of gained is filtrated to get into powder presoma, is dried overnight under the conditions of 70 DEG C,
Then the h of roasting 6 under the conditions of 550 DEG C of air atmospheres, that is, obtain the catalyst of the present invention.
Catalyst obtained in 0.3 gram is added in 3.2 grams of glycerine, mixed liquor is formed；Mixed liquor is heated to into 220 DEG C, place
Manage 30 min；10 grams of corn oils are added in mixed liquor of the glycerine with catalyst；In 220 DEG C of reaction temperature, 500 rpm
Mixing speed, react 24 hours.The conversion ratio of corn oil is 100%, and monoglyceride yield is 42.9%, and diglyceride yield is
57.1%.Atomic absorption spectroscopy is carried out to glycerine and catalyst mixed liquid, the Ca being lost in is not detected by.
Embodiment 2
By 2 grams of SBA-16,2.1 grams of Sr (NO3)2With 10 milliliters of water mixing, grinding is uniformly；30 milliliters of water are added, 100
DEG C night is flow through next time；The mixed liquor of gained is filtrated to get into powder presoma, is dried overnight under the conditions of 70 DEG C, Ran Hou
The h of roasting 6 under the conditions of 550 DEG C of air atmospheres, that is, obtain the catalyst of the present invention.
Catalyst obtained in 0.3 gram is added in 3.2 grams of glycerine, mixed liquor is formed；Mixed liquor is heated to into 200 DEG C, place
Manage 30 min；10 grams of corn oils are added in mixed liquor of the glycerine with catalyst；In 200 DEG C of reaction temperature, 500 rpm
Mixing speed, react 5 hours.The conversion ratio of corn oil is 98.7%, and monoglyceride yield is 23.7%, and diglyceride yield is
75.0%.Atomic absorption spectroscopy is carried out to the mixed liquor of glycerine and catalyst, the Ca being lost in is not detected by.
Embodiment 3
By 2 grams of KIT-6,2.3 grams of Ca (NO3)2 .4H2O and 10 milliliter of n-hexane mixed grinding is uniform；Add 30 milliliters
N-hexane, at 70 DEG C night is flow through next time；The mixed liquor of gained is filtrated to get into powder presoma, is dried under the conditions of 70 DEG C
Overnight, the then h of roasting 6 under the conditions of 550 DEG C of air atmospheres, that is, obtain the catalyst of the present invention.
Catalyst obtained in 0.3 gram is added in 3.2 grams of glycerine, mixed liquor is formed；Mixed liquor is heated to into 220 DEG C, place
Manage 30 min；10 grams of corn oils are added in mixed liquor of the glycerine with catalyst；In 220 DEG C of reaction temperature, 500 rpm
Mixing speed, react 5 hours.The conversion ratio of corn oil is 100%, and monoglyceride yield is 21.3%, and diglyceride yield is
78.7%.Atomic absorption spectroscopy is carried out to the mixed liquor of glycerine and catalyst, the Ca being lost in is not detected by.
Embodiment 4
By 2 grams of SBA-15,2.3 grams of Ca (NO3)2 .4H2O and 10 milliliter of n-hexane mixed grinding is uniform；Add 30 milliliters
N-hexane, flow through night next time at 70 DEG C；The mixed liquor of gained is filtrated to get powder presoma, is dried under the conditions of 70 DEG C
Overnight, the then h of roasting 6 under the conditions of 550 DEG C of air atmospheres, that is, obtain the catalyst of the present invention.
Catalyst obtained in 0.3 gram is added in 3.2 grams of glycerine, mixed liquor is formed；Mixed liquor is heated to into 220 DEG C, place
Manage 30 min；10 grams of corn oils are added in mixed liquor of the glycerine with catalyst；In 220 DEG C of reaction temperature, 500 rpm
Mixing speed, react 5 hours.The conversion ratio of corn oil is 98.1%, and monoglyceride yield is 23.3%, and diglyceride yield is
74.8%.Atomic absorption spectroscopy is carried out to the mixed liquor of glycerine and catalyst, the Ca being lost in is not detected by.
Claims (6)
1. a kind of preparation method of solid base catalyst, it is characterised in that concretely comprise the following steps：
（1）According to the amount of mesoporous material supported alkaline earth metal, alkali salt, mesoporous material and solvent are weighed, mixed grinding is extremely
Form paste mixture；Wherein, the mesoporous material is the one kind in SBA-15, SBA-16, KIT-6, or wherein several mixed
Compound；The load capacity of alkaline-earth metal is between 4% to the 20% of mesoporous material quality；It is oxidation as the alkaline-earth metal of active component
One kind of thing MgO, CaO, SrO；
（2）Then paste mixture is added in solvent, is stirred, flowed back at boiling temperature overnight；
（3）Jing is filtered, and obtains white solid, is dried, and then roasting 5-8 is little under the conditions of 450-600 DEG C, air atmosphere
When.
2. the preparation method of solid base catalyst according to claim 1, it is characterised in that described alkali salt is
Mg(NO3)2、Ca(NO3)2、Sr(NO3)2、Ca(CH3COO)2、Mg(CH3COO)2Or Sr (CH3COO)2In one kind, or wherein
Several mixtures.
3. the preparation method of solid base catalyst according to claim 1 and 2, it is characterised in that：It is step 1, molten described in 2
Agent is water or n-hexane.
4. the solid base catalyst for being prepared by one of claim 1-3 preparation method.
5. application of the solid base catalyst as claimed in claim 4 in glycerolysis reaction, it is characterised in that including following
Process：
Solid base catalyst is mixed in addition reactor with glycerine, 25-40 min are processed at the reaction temperatures, be subsequently adding
Vegetable oil, is 180-240 DEG C in temperature, and mixing speed is under 300-1000 rpm, to react 1-24 h；
Wherein, the mol ratio of glycerine and vegetable oil is 2:1-10:1；The consumption of solid base catalyst is the 3%- of plant oil quality
10%。
6. application according to claim 5, it is characterised in that the vegetable oil is soya-bean oil, corn oil, palm oil, cottonseed
One or more mixture in oil, olive oil.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101302433A (en) * | 2008-06-20 | 2008-11-12 | 华东理工大学 | Method for preparing biodiesel by super base-catalyzed ester exchange reaction of lipid and low-carbon alcohol |
| CN101380570A (en) * | 2008-10-24 | 2009-03-11 | 吉林大学 | Load type solid base catalyst for preparing biology diesel fuel and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101302433A (en) * | 2008-06-20 | 2008-11-12 | 华东理工大学 | Method for preparing biodiesel by super base-catalyzed ester exchange reaction of lipid and low-carbon alcohol |
| CN101380570A (en) * | 2008-10-24 | 2009-03-11 | 吉林大学 | Load type solid base catalyst for preparing biology diesel fuel and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 介孔材料在催化剂制备生物柴油中的研究进展;王瑞，等;《化工进展》;20101231;第29卷;第70页左栏第1段至第71页左栏倒数第2段及表1 * |
| 制备生物柴油的负载型固体碱催化剂研究进展;常瑶，等;《化工新型材料》;20130731;第41卷(第7期);第10-12页 * |
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