CN106362723A - Metal oxide catalyst, and preparation method and application thereof - Google Patents
Metal oxide catalyst, and preparation method and application thereof Download PDFInfo
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- CN106362723A CN106362723A CN201610643176.8A CN201610643176A CN106362723A CN 106362723 A CN106362723 A CN 106362723A CN 201610643176 A CN201610643176 A CN 201610643176A CN 106362723 A CN106362723 A CN 106362723A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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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
Abstract
The invention specifically relates to a metal oxide catalyst, and a preparation method and application thereof, i.e., large-pore-diameter mesoporous metal oxide catalyst and a preparation method there and application of the catalyst to catalytic synthesis of higher fatty acid--biodiesel, belonging to the technical field of preparation of higher fatty acid. The preparation method comprises the following steps: (1) preparing a mixed solution from ethanol and N-butyl titanate; (2) adding an aqueous solution of cerium nitrate and an aqueous solution of transition metal oxide into the mixed solution and carrying out a reaction under stirring in an acidic environment; and (3) subjecting the mixed solution and a transition metal salt to a reaction in an oil bath so as to obtain the metal oxide catalyst. According to the invention, the large-pore-diameter mesoporous metal oxide catalyst is prepared from N-butyl titanate, ethanol, rare earth nitrate and the transition metal salt and applied to preparation of biodiesel; and the prepared catalyst is simple to prepare, good in catalytic activity, high in product selectivity, convenient to recover and good in recycling performance.
Description
Technical field
The present invention relates to high-grade aliphatic ester preparing technical field is and in particular to a kind of large aperture mesoporous metal oxide is urged
Agent and preparation method thereof and the method synthesizing high-grade aliphatic ester biodiesel with this catalyst.
Background technology
High-grade aliphatic ester can be used as biodiesel.This bio-fuel can substitute fossil diesel fuel, has ideal
Combustibility, the many index such as calorific value, combustion stability, low-temperature startup and be superior to petrifaction diesel, it is also only simultaneously
The replacing fuel oil that the one health effect detection entirely reaching U.S. Clean Air Act defined requires.Biodiesel is because having low-sulfur
Amount, low arene content, fabulous lubricity, renewable, environmentally friendly the advantages of and receive much concern.Thus its successful exploitation
Oil crisis can be alleviated with utilization, be economic development injection new vitality.
Traditional biodiesel production method is with the liquid acid such as sulphuric acid, hydrochloric acid, phosphoric acid, Fluohydric acid. and potassium hydroxide, hydrogen-oxygen
Changing the alkali such as sodium, sodium alkoxide is catalyst, does not only have strong corrosivity to equipment, separates difficulty, and produce big when Protic Acid Catalyzed
Amount waste liquid, and during base catalysiss, raw material is had and be relatively strict with.So as to application receives under the overall situation advocating green chemical industry
Considerable restraint.
Using solid metal oxide as catalyst and with metal-oxide for carrier prepare catalyst synthetic reaction when
Reaction condition is gentle, and post catalyst reaction can be easily separated, and reusability is high, and easily adopts automatic continuous production, to setting
Standby corrosion-free, environmentally safe, thus there is applications well prospect.
Content of the invention
The invention provides a kind of preparation method and application of large aperture mesoporous metal oxide catalyst, this catalyst use
In catalyzed synthesis of fatty acid ester, efficiently, environmental pollution is little, recovery is easy, Repeatability good.
A kind of preparation method of large aperture mesoporous metal oxide catalyst, comprises the steps:
(1) mixed solution is formed for raw material with ethanol, tetrabutyl titanate；
(2) rare earth nitrate aqueous solution is added in described mixed solution with transition metal saline solution, and under sour environment
Stirring is carried out；
(3) after described mixed solution and transition metal salt react in oil bath and terminate, ageing, roasting obtains final product described metal-oxide
Catalyst.
Metal-oxide is the new greenization reagent of a class, as reaction catalyst, can be lifted reaction activity and
Selectivity.The research of catalyst biodiesel synthesis that can be sour as an alternative.It is applied to preparing of biodiesel anti-
Should, easy and simple to handle, catalysis activity is good, selectivity of product is high, recovery is convenient, it is good to recycle performance.
We are based on solid-state nmr analysis and research and show that acidity and steric effect are its highly active reasons, and the present invention adopts metatitanic acid
N-butyl, alcohol, rare earth and transition metal salt are raw material, using the catalyst of sol-gel process preparation, not only have certain acid
Intensity, simultaneously gained catalyst there is large aperture and central hole structure, reduce the impact to catalysis activity for the internal diffusion, both make jointly
Result makes catalyst activity that the present invention prepares and stability all significantly improve, and higher fatty acids are prepared in catalysis
Yield more than 80%, the purity of product more than 98%, the equal recoverable of catalyst, after repeating to test 5 times, measure produce
Rate is floated all within 5%.
Preferably, described rare earth nitrate is la (no3)3·6h2o、sm(no3)3·6h2o、ce(no3)3·6h2o、pr
(no3)3·6h2O or nd (no3)3·6h2o；Described transition metal salt is ni (no3)2·6h2o、fe(no3)3·9h2o、co
(no3)2·6h2o、cu(no3)2·3h2o、agno3、mncl2、zncl2Or zrocl2·8h2o.Prepared using this combination
Its catalysis of catalyst prepares the yield of high-grade aliphatic ester more than 80%, and the purity of product is more than 98%.
Most preferably, described rare earth nitrate is ce (no3)3·6h2O, transition metal salt is fe (no3)3·9h2O, at this
Its catalysis of catalyst preparing under optimum material combination prepares the yield of high-grade aliphatic ester more than 90%, product
Purity is more than 98%.
Preferably, the amount of ethanol described in step (1) and the material of tetrabutyl titanate is than for 4:1.
Further preferably, tetrabutyl titanate, rare earth nitrate (cerous nitrate) and the material of transition metal salt in step (2)
Amount ratio is 8:1:1.
Preferred by above-mentioned tetrabutyl titanate, rare earth nitrate, transition metal salt and proportioning in the present invention, prepare
Catalyst activity significantly improve, decrease the usage amount of catalyst in catalytic reaction；Reaction terminates rear catalyst and easily returns
Receive and recycle, catalysis activity is stable, catalytic effect keeps good.
Preferably, the temperature forming mixed solution reaction in step (1) is room temperature, the time is 15 ~ 30min；Step (2)
Middle configuration mixed solution reaction temperature is room temperature；In step (3), the temperature of oil bath reaction is 50-100 DEG C, and the time is 18-30h；
It is further preferred that step (1) reaction need to be stirred at 15-40 DEG C and be carried out, the time is 15 ~ 30min；Step (2) often needs
Progressively Deca one by one under temperature, and plus 2ml concentrated hydrochloric acid, make reactant be in sour environment；In step (3), oil bath reaction temperature is 60
DEG C, mixing time 24h.
Post-processing step described in catalyst preparation process is: place reaction liquid into culture dish evaporate into dry, at 100 DEG C
Overnight dry, collect residue and place 300-600 DEG C of calcining 5h in Muffle furnace, final described product.Further preferably forge
Burn temperature and be 500 DEG C.
The present invention also provides the metal oxide catalyst that a kind of preparation method as described herein prepares.
The present invention also provides a kind of method preparing fatty acid ester using such as described metal oxide catalyst catalysis, including
Following steps:
(1) with fatty acid, alcohol as raw material, described metal-oxide as catalyst, in 60 ~ 110 DEG C of oil baths react 2 ~ 6h；
(2) cooling after reaction terminates, catalyst is layered with reaction system, and product sucking filtration separation solid catalyst is washed through ether
Wash, be dried after can be directly used for next secondary response.Excessive methanol is evaporated off.Vacuum distillation obtains biodiesel.
Described fatty acid refers to Palmic acid, Oleic acid etc., and described alcohol is mainly methanol, ethanol, propanol, and the amount of material ratio is for 1:
10 ~ 14, the amount ratio of optimum material elects 1:12 as.
Preferably, the consumption of metal oxide catalyst is (4 of fatty acid quality in reaction in described esterification
Wt%-6 wt%).
Step (1) reacts 2h most preferably in 90 DEG C of oil baths.Fatty acid ester is prepared in catalysis under the combination of above-mentioned optimum condition
Yield and purity be attained by a high value.
Compared with prior art, the invention has the following beneficial effects:
The present invention prepares metal oxide catalyst with tetrabutyl titanate, ethanol and transition metal salt for raw material, and is applied
In the preparation reaction of high-grade aliphatic ester, easy and simple to handle, catalysis activity is good, selectivity of product is high, recovery is convenient, recycling
Can be good.Outstanding advantages of the present invention are that catalysis activity is good, post processing is simple, it is good to recycle performance, belong to Green Chemistry.
Specific embodiment
Raw materials used in following examples it is commercial goods.
Embodiment 1
, the preparation method of catalyst is as follows taking cefetio as a example:
(1) ethanol and tetrabutyl titanate are stirred 15 ~ 30min under room temperature and form mixed solution；
(2) cerous nitrate aqueous solution and fe (no3) 3 9h2o aqueous solution are gradually added mixed solution one by one, plus appropriate concentrated hydrochloric acid
Make reaction be in acid condition, reaction system is positioned in oil bath, is stirred overnight.
The amount of ethanol is about 4-5 times of tetrabutyl titanate, and the mol ratio of tetrabutyl titanate, cerous nitrate and transition metal salt is
8:1:1, oil bath reaction temperature is 60 DEG C, and the response time is 24h.
(3) after stirring reaction terminates, place reaction liquid into culture dish and evaporate into dry, overnight dry at 100 DEG C, collect surplus
Excess places 500 DEG C of calcining 5h in Muffle furnace, final product that must be described.
Replace the rare earth nitrate in above step (1) and transition metal salt prepare different catalyst:
cefetio、ceagtio、cecotio、cecutio、cezrtio、cezntio、lafetio、smfetio、ndfetio、
prfetio.Catalyze and synthesize high-grade aliphatic ester in following examples.
Embodiment 2-14
To in the there-necked flask of 100 ml equipped with constant pressure funnel and reflux condensing tube, sequentially add Palmic acid 7.68g, methanol
11.52g, catalyst 0.38g, are placed on reacting by heating 2.0h in 90 DEG C of oil baths.Reaction terminate after cooling, catalyst with anti-
Answer system layering, product sucking filtration separation solid catalyst, after ether washing, drying, can be directly used for next secondary response.It is evaporated off
Excessive methanol.Vacuum distillation obtains biodiesel, and gas chromatogram carries out purity detecting.
From the variety classes catalyst of preparation in embodiment 1, by examples detailed above operation, obtain esterification result such as table
Shown in 1.
Table 1
| Catalyst type | Yield/% | Purity/% |
| cefetio | 92.1 | 99.5 |
| cetio | 72.5 | 98.0 |
| fetio | 82.5 | 98.2 |
| ceagtio | 80.6 | 99.3 |
| cecotio | 81.4 | 99.1 |
| cezntio | 83.6 | 98.4 |
| cecutio | 82.2 | 98.9 |
| cezrtio | 85.4 | 98.5 |
| zrfetio | 85.7 | 98.2 |
| smfetio | 90.1 | 99.2 |
| lafetio | 88.5 | 99.4 |
| prfetio | 87.8 | 98.9 |
| ndfetio | 86.9 | 98.3 |
Embodiment 15-19
To in the there-necked flask of 100 ml equipped with constant pressure funnel and reflux condensing tube, sequentially add Palmic acid 7.68g, methanol
11.52g, catalyst 0.38g, are placed on reacting by heating 2.0h in 90 DEG C of oil baths.Reaction terminate after cooling, catalyst with anti-
Answer system layering, product sucking filtration separation solid catalyst, after ether washing, drying, can be directly used for next secondary response.It is evaporated off
Excessive methanol.Vacuum distillation obtains biodiesel, and gas chromatogram carries out purity detecting.
Metal oxide catalyst from the different metal proportioning of preparation in embodiment 1 continues esterification, obtains ester
Change reaction result as shown in table 2.
Table 2
| Metal molar proportioning (ce:fe) | Yield/% | Purity/% |
| 1:1 | 92.1 | 99.5 |
| 3:4 | 81.0 | 98.2 |
| 2:1 | 87.5 | 99.2 |
| 1:3 | 87.3 | 99.4 |
| 1:2 | 86.7 | 98.7 |
Embodiment 20-24
To in the there-necked flask of 100 ml equipped with constant pressure funnel and reflux condensing tube, sequentially add Palmic acid 7.68g, catalysis
Agent 0.38g, is placed on reacting by heating 2.0h in 90 DEG C of oil baths, and reaction cools down after terminating, and catalyst is layered with reaction system,
Product sucking filtration separation solid catalyst, can be directly used for next secondary response after ether washing, drying.Excessive methanol is evaporated off.
Vacuum distillation obtains biodiesel, and gas chromatogram carries out purity detecting.The amount ratio changing alcohol acid substance obtains esterification result such as
Shown in table 3.
Table 3
| The amount ratio of alcohol acid substance | Yield/% | Purity/% |
| 1:8 | 81.7 | 98.9 |
| 1:10 | 86.2 | 98.8 |
| 1:12 | 92.1 | 99.5 |
| 1:14 | 90.9 | 98.9 |
| 1:16 | 87.5 | 99.1 |
Embodiment 25-28
To in the there-necked flask of 100 ml equipped with constant pressure funnel and reflux condensing tube, sequentially add Palmic acid 7.68g, first
Alcohol 11.52g, catalyst 0.38g, are placed on reacting by heating in 90 DEG C of oil baths, react cooling, catalyst and reaction after terminating
System layering, product sucking filtration separation solid catalyst, can be directly used for next secondary response after ether washing, drying.It was evaporated off
The methanol of amount.Vacuum distillation obtains biodiesel, and gas chromatogram carries out purity detecting.
It is as shown in table 4 that the change differential responses time obtains esterification result.
Table 4
| Response time/h | Yield/% | Purity/% |
| 0.5 | 73.8 | 98.9 |
| 1 | 84.1 | 99.1 |
| 1.5 | 88.8 | 98.7 |
| 2 | 92.1 | 99.5 |
Embodiment 29-32
To in the there-necked flask of 100 ml equipped with constant pressure funnel and reflux condensing tube, sequentially add Palmic acid 7.68g, first
Alcohol 11.52g, catalyst 0.38g, are placed on reacting by heating 2h in 90 DEG C of oil baths, reaction terminate after cooling, catalyst with anti-
Answer system layering, product sucking filtration separation solid catalyst, after ether washing, drying, can be directly used for next secondary response.It is evaporated off
Excessive methanol.Vacuum distillation obtains biodiesel, and gas chromatogram carries out purity detecting.
It is as shown in table 5 that change catalyst difference sintering temperature obtains esterification result.
Table 5
| Sintering temperature/DEG C | Yield/% | Purity/% |
| 300 | 66.8 | 98.9 |
| 400 | 77.1 | 99.1 |
| 500 | 92.1 | 99.5 |
| 600 | 81.3 | 99.0 |
After above reaction terminates, the equal recoverable of catalyst, after repeating to test five times, measure yield float all 5 % with
Interior.
Certainly, those of ordinary skill in the art it should be appreciated that above embodiment be intended merely to illustrate the present invention,
And it is not intended as limitation of the invention, as long as in the essential scope of the present invention, to the change of embodiment described above, modification
All will fall in the range of claims of the present invention.
Claims (10)
1. a kind of preparation method of metal oxide catalyst is it is characterised in that comprise the steps:
(1) mixed solution is formed for raw material with ethanol, tetrabutyl titanate；
(2) rare earth nitrate aqueous solution is added in described mixed solution with transition metal saline solution, and under sour environment
Stirring is carried out；
(3) after described mixed solution and transition metal salt react in oil bath and terminate, ageing, roasting obtains final product described metal-oxide
Catalyst.
2. according to claim 1 the preparation method of metal oxide catalyst it is characterised in that described rare earth nitrate is
la(no3)3·6h2o、sm(no3)3·6h2o、ce(no3)3·6h2o、pr(no3)3·6h2O or nd (no3)3·6h2o；Described mistake
Crossing slaine is ni (no3)2·6h2o、fe(no3)3·9h2o、co(no3)2·6h2o、cu(no3)2·3h2o、agno3、mncl2、
zncl2Or zrocl2·8h2o.
3. according to claim 2 the preparation method of metal oxide catalyst it is characterised in that described rare earth nitrate is
ce(no3)3·6h2O, transition metal salt is fe (no3)3·9h2o.
4. according to claim 1 the preparation method of metal oxide catalyst it is characterised in that used by described sour environment
Acid is hydrochloric acid, nitric acid, oxalic acid, citric acid, ascorbic acid.
5. according to claim 1 metal oxide catalyst preparation method it is characterised in that described ethanol and metatitanic acid just
The amount of the material of butyl ester is than for 4:1.
6. according to claim 1 the preparation method of metal oxide catalyst it is characterised in that titanium described in step (2)
The amount of the material of sour N-butyl, rare earth nitrate and transition metal salt is than for 8:1:1.
7. according to claim 1 the preparation method of metal oxide catalyst it is characterised in that step (1) reaction need to be
Under room temperature, stirring is carried out, and the time is 15 ~ 30min；Step (2) rare earth nitrate aqueous solution is needed one by one with transition metal saline solution
Progressively Deca, and acid adding, make reactant be in sour environment；In step (3), oil bath reaction temperature is 50-100 DEG C, mixing time
For 18-30h.
8. the metal oxide catalyst that the arbitrary described preparation method of claim 1 ~ 7 prepares.
9. one kind prepares high-grade aliphatic ester method using metal oxide catalyst catalysis described in claim 8, and its feature exists
In comprising the steps:
(1) with fatty acid, alcohol as raw material, metal oxide catalyst described in claim 8 as catalyst, in 60 ~ 110 DEG C of oil baths
Reaction 2 ~ 6h；
(2) cooling after reaction terminates, catalyst is layered with reaction system, and product sucking filtration separation solid catalyst is washed through ether
Wash, be dried after can be directly used for next secondary response.
10. 9 methods describeds are wanted according to right it is characterised in that described acid is saturation or the unsaturated fatty acid of c8-c20；Described
Alcohol is methanol, ethanol or propanol；For 1:10 ~ 14, described catalyst amount is fatty acid quality to the amount of fatty acid and alcohol matter ratio
3%-6%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20200122127A1 (en) * | 2018-10-19 | 2020-04-23 | Research & Business Foundation Sungkyunkwan University | Catalyst for chemical looping combustion |
| CN112630199A (en) * | 2020-11-10 | 2021-04-09 | 河北大学 | Alloy nano-cluster-based folic acid content detection method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101041130A (en) * | 2007-04-12 | 2007-09-26 | 上海三瑞化学有限公司 | Catalysts for solid base for producing biodiesel |
| US20110185625A1 (en) * | 2008-08-21 | 2011-08-04 | Sbi Fine Chemicals Inc. | Solid, heterogeneous catalysts and methods of use |
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2016
- 2016-08-09 CN CN201610643176.8A patent/CN106362723B/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101041130A (en) * | 2007-04-12 | 2007-09-26 | 上海三瑞化学有限公司 | Catalysts for solid base for producing biodiesel |
| US20110185625A1 (en) * | 2008-08-21 | 2011-08-04 | Sbi Fine Chemicals Inc. | Solid, heterogeneous catalysts and methods of use |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20200122127A1 (en) * | 2018-10-19 | 2020-04-23 | Research & Business Foundation Sungkyunkwan University | Catalyst for chemical looping combustion |
| CN112630199A (en) * | 2020-11-10 | 2021-04-09 | 河北大学 | Alloy nano-cluster-based folic acid content detection method |
| CN112630199B (en) * | 2020-11-10 | 2022-10-21 | 河北大学 | Alloy nano-cluster-based folic acid content detection method |
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