CN113275015A - Biodiesel acid-base bifunctional magnetic nano catalyst, and preparation method and application thereof - Google Patents
Biodiesel acid-base bifunctional magnetic nano catalyst, and preparation method and application thereof Download PDFInfo
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- CN113275015A CN113275015A CN202110572793.4A CN202110572793A CN113275015A CN 113275015 A CN113275015 A CN 113275015A CN 202110572793 A CN202110572793 A CN 202110572793A CN 113275015 A CN113275015 A CN 113275015A
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- 239000003225 biodiesel Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 14
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000001354 calcination Methods 0.000 claims abstract description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000012018 catalyst precursor Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 9
- 239000008158 vegetable oil Substances 0.000 claims description 9
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical class Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 239000001110 calcium chloride Substances 0.000 claims description 7
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 7
- 239000000084 colloidal system Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 20
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 239000003549 soybean oil Substances 0.000 abstract description 6
- 235000012424 soybean oil Nutrition 0.000 abstract description 6
- 229910003145 α-Fe2O3 Inorganic materials 0.000 abstract description 5
- 229910006297 γ-Fe2O3 Inorganic materials 0.000 abstract description 5
- 238000011161 development Methods 0.000 abstract description 4
- 230000005389 magnetism Effects 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 4
- 229910052723 transition metal Inorganic materials 0.000 abstract description 4
- 150000002191 fatty alcohols Chemical class 0.000 abstract description 3
- 239000004014 plasticizer Substances 0.000 abstract description 3
- 230000000087 stabilizing effect Effects 0.000 abstract description 3
- 238000010348 incorporation Methods 0.000 abstract description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract 2
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract 1
- 239000001569 carbon dioxide Substances 0.000 abstract 1
- 239000002283 diesel fuel Substances 0.000 abstract 1
- 230000009977 dual effect Effects 0.000 abstract 1
- 239000002585 base Substances 0.000 description 18
- 239000011575 calcium Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000000446 fuel Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
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- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 235000019482 Palm oil Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
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- 238000010992 reflux Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- UPWOEMHINGJHOB-UHFFFAOYSA-N cobalt(III) oxide Inorganic materials O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000008162 cooking oil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- 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
- B01J23/78—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 alkali- or alkaline earth metals
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
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Abstract
The invention discloses a biodiesel acid-base bifunctional magnetic nano-catalyst, a preparation method and application thereof. In the method, a transition metal element Co is doped into Fe with acid-base dual functions by a hydrothermal and calcination method2O3Mixing CaO, Co is doped into CaO, so that Ca2+Increased stability, Fe2O3For Ca2+Also has certain stabilizing effect, and the two simultaneously relieve Ca2+The loss of the carbon dioxide gas is reduced,the catalytic activity and the service life of the catalyst are improved. And the incorporation of Co results in Fe2O3From alpha-Fe2O3Conversion to gamma-Fe2O3Thereby the catalyst has magnetism and can be recycled through magnetic recovery. In addition, the catalyst can effectively catalyze the conversion of soybean oil into biodiesel, and the yield can reach 98.0%. In addition, the prepared biodiesel can be used as diesel fuel, is developed into additional value products such as fatty alcohol and green plasticizer, and has great industrial application development potential.
Description
Technical Field
The invention belongs to the technical field of biomass energy, and particularly relates to a biodiesel acid-base bifunctional magnetic nano catalyst Co/Fe2O3A preparation method and application of CaO.
Background
Fossil fuels are the most commonly used energy source, accounting for 80% of the world's energy demand. However, fossil energy is not renewable and as human demand for energy increases, the search for alternative energy has become a focus of worldwide attention, and the proposition of the "carbon peak-to-peak, carbon neutralization" goal in our country indicates that biodiesel is likely to become the most potential alternative fuel in the near future. At present, biodiesel is mainly synthesized by carrying out ester exchange reaction on renewable resources such as animal and vegetable oil, waste cooking oil, microalgae and the like by utilizing a homogeneous or heterogeneous catalyst. Transesterification of homogeneous catalysts is the most common and most commercial technique, but has problems of environmental pollution and high recovery cost. Heterogeneous catalysts can overcome this problem by being easily separated and recovered. The conventional solid acid catalyst has high tolerance to the acid value and moisture of raw oil, but has a slow reaction rate, and the solid base catalyst has a fast reaction rate, but has high requirements on the acid value and moisture of the raw oil, otherwise, saponification reaction can occur, separation is affected, and catalyst loss can be caused.
The CaO has the advantages of easily available raw materials, wide sources, low cost, high catalytic activity and the like, and is widely applied to the catalytic preparation of biodiesel. However, when pure CaO directly catalyzes the transesterification reaction, lattice oxygen radicals on the surface of the CaO easily form hydrogen bonds with methanol or glycerol, the viscosity of the glycerol is increased, and a suspension is formed with the CaO, so that the problems of loss of active components of the catalyst, difficulty in separation and the like are caused. Therefore, the development of the magnetic acid-base bifunctional heterogeneous calcium-based catalyst which has high stability, strong active sites, acid and moisture resistance, easy separation and recovery and can be recycled for preparing the biodiesel more efficiently has certain research significance.
Disclosure of Invention
In order to solve the problems that the active component of the pure CaO serving as the catalyst is easy to lose and difficult to separate, and the like, the invention dopes the transition metal element Co into the mixed metal oxide Fe2O3Doping Co into CaO on CaO, causing the CaO lattice to deform, Ca2+Increased stability, and Fe2O3For Ca2+Also has certain stabilizing effect, and the two simultaneously relieve Ca2+The loss of the catalyst improves the catalytic activity and the service life of the catalyst. In addition, Co is doped into Fe2O3In (1), make Fe2O3Is transformed from alpha-Fe2O3Conversion to gamma-Fe2O3And the catalyst is also magnetic.
The technical scheme provided by the invention is as follows:
an acid-base bifunctional magnetic nano catalyst for biodiesel, whose structure is Co/Fe2O3-CaO; wherein the molar ratio of Co to Ca is 0.2: 1-0.6: 1.
The molar ratio of Co to Ca is preferably 0.4:1 to 0.5: 1.
A preparation method of a biodiesel acid-base bifunctional magnetic nano catalyst comprises the following steps:
1) adding CaCl2And FeCl3·6H2O salt solution in a ratio of 1: 1, adding CoSO4·7H2O, wherein the molar ratio of Co to Ca is 0.2: 1-0.6: 1, dissolving, then dropwise adding a NaOH solution to form a colloid, continuously stirring for 20-60 min, transferring to a reaction kettle, heating to 180 ℃, carrying out hydrothermal reaction for 9-13 h, filtering, and drying at 60-120 ℃ for 6-24 h to obtain a catalyst precursor;
2) calcining the catalyst precursor obtained in the step (1) at 500-900 ℃ for 1-4 h to obtain a catalyst Co/Fe2O3-CaO。
The method preferably selects the molar ratio of Co to Ca of 0.4: 1-0.5: 1.
The method preferably comprises the step 1) of adding CoSO4·7H2And continuously stirring for 30-50 min after the O is stirred and dissolved.
The method preferably adopts the hydrothermal reaction in the step 1) for 10-12 hours.
The method preferably comprises the step 1) of drying at 90-110 ℃ for 10-12 h to obtain the catalyst precursor.
In the method, the catalyst Co/Fe is obtained by calcining for 1-3 h at 600-800 ℃ in the step 2) preferably2O3-CaO。
The invention relates to application of a biodiesel acid-base bifunctional magnetic nano catalyst in biodiesel preparation.
Carrying out ester exchange reaction on methanol and vegetable oil to prepare biodiesel, wherein the molar ratio of the methanol to the vegetable oil is 12: 1-18: 1; the heating method is heating in water bath to 60-80 ℃; the adding amount of the catalyst is 2-4% of the mass of the vegetable oil; the heating time is 90-150 min.
Compared with the prior art, the invention has obvious technical advantages and beneficial effects. According to the technical scheme, the invention has the following advantages:
(1) co element is doped into active components CaO and Fe2O3In addition, the loss of active components is reduced, the catalytic activity and the service life of the catalyst are improved, the yield of the biodiesel is improved, and the catalyst is excellentGood biodiesel catalysts;
(2) the invention dopes Co element into Fe2O3In (1), make Fe2O3Is transformed from alpha-Fe2O3Conversion to gamma-Fe2O3The catalyst has magnetism, can realize solid-liquid separation only by simply applying an external magnetic field, simplifies the subsequent complicated product separation steps of the traditional solid base, improves the production efficiency of the biodiesel, and has better industrial application value;
(3) the acid-base bifunctional magnetic nano catalyst for biodiesel, provided by the invention, has stronger acid resistance and water resistance, can be suitable for preparing biodiesel from high-acid-value raw materials, expands the application range of the raw materials, and has better industrial application prospect.
(4) The biodiesel prepared by using the acid-base bifunctional magnetic nano catalyst for biodiesel has the characteristics of higher cetane number, lower calorific value, low sulfur content, low filter point and the like, conforms to the EDIN51606 standard, and has better combustion performance, low-temperature starting performance, excellent environmental protection performance and the like. The composite material can be used as engine fuel and aviation fuel, can be developed into additional value products such as fatty alcohol and green plasticizer, and has great industrial development potential and good market application prospect.
The method dopes a transition metal element Co into Fe by a hydrothermal and calcination method2O3And CaO, CaO having basic active sites, Fe2O3Has acid active sites, Co is doped into CaO to deform CaO crystal lattice, and Ca2+Increased stability, in addition to Fe2O3For Ca2+Also has certain stabilizing effect, and the two simultaneously relieve Ca2+The loss of the catalyst improves the catalytic activity and the service life of the catalyst. And the incorporation of Co results in Fe2O3From alpha-Fe2O3Conversion to gamma-Fe2O3Therefore, the catalyst has magnetism and can be recycled by magnetic recovery, and the post-treatment process of the biodiesel is simplified. The catalyst can effectively catalyze the conversion of soybean oil into soybean oilThe yield of the biodiesel can reach 98.0 percent under the optimal preparation and implementation conditions, and the yield is higher than that of Fe under the same reaction conditions2O3-high CaO; in addition, the prepared biodiesel can be used as engine fuel and aviation fuel, can be developed into additional value products such as fatty alcohol and green plasticizer, and has great industrial application development potential and good market application prospect.
Drawings
FIG. 1 shows examples 2, 3 and 4 and Fe without Co doping2O3CaO catalyst and Fe2O3And XRD test pattern of CaO standard PDF card;
FIG. 2 shows examples 2, 3 and 4 and Fe without Co doping2O3-a VSM test chart of the CaO catalyst;
FIG. 3 is a SEM test chart of example 3 of the present invention;
FIG. 4 shows NH in example 3 of the present invention3TPD and CO2-a TPD test pattern.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
A preparation method of a biodiesel magnetic solid base catalyst comprises the following steps:
(1) adding CaCl2And FeCl3·6H2O salt solution in a ratio of 1: 1, adding CoSO4·7H2O, wherein the molar ratio of Co to Ca is 0.2:1, dropwise adding a sodium hydroxide solution to form a colloid after stirring and dissolving, continuously stirring for 20min, transferring to a reaction kettle, heating to 180 ℃ for hydrothermal reaction for 9h, filtering, and drying at 60 ℃ for 24h to obtain a catalyst precursor;
(2) calcining the catalyst precursor obtained in the step (1) at 500 ℃ for 1h to obtain a catalyst Co0.2/Fe2O3-CaO；
Example 2
A preparation method of a biodiesel magnetic solid base catalyst comprises the following steps:
1) adding CaCl2And FeCl3·6H2O salt solution in a ratio of 1: 1, adding CoSO4·7H2O, wherein the molar ratio of Co to Ca is 0.4:1, dropwise adding a sodium hydroxide solution to form a colloid after stirring and dissolving, continuously stirring for 30min, transferring to a reaction kettle, heating to 180 ℃ for hydrothermal reaction for 10h, filtering, and drying at 90 ℃ for 12h to obtain a catalyst precursor;
(2) calcining the catalyst precursor obtained in the step (1) at 600 ℃ for 1h to obtain a catalyst Co0.4/Fe2O3-CaO；
Example 3
A preparation method of a biodiesel magnetic solid base catalyst comprises the following steps:
(1) adding CaCl2And FeCl3·6H2O salt solution in a ratio of 1: 1, adding CoSO4·7H2O, wherein the molar ratio of Co to Ca is 0.45: 1, dropwise adding a sodium hydroxide solution to form a colloid after stirring and dissolving, continuously stirring for 40min, transferring to a reaction kettle, heating to 180 ℃ for hydrothermal reaction for 11h, filtering, and drying at 100 ℃ for 11h to obtain a catalyst precursor;
(2) calcining the catalyst precursor obtained in the step (1) at 700 ℃ for 2h to obtain a catalyst Co0.45/Fe2O3-CaO；
Example 4
A preparation method of a biodiesel magnetic solid base catalyst comprises the following steps:
1) adding CaCl2And FeCl3·6H2O salt solution in a ratio of 1: 1, adding CoSO4·7H2O, wherein the molar ratio of Co to Ca is 0.5:1, dropwise adding a sodium hydroxide solution to form a colloid after stirring and dissolving, continuously stirring for 50min, transferring to a reaction kettle, heating to 180 ℃ for hydrothermal reaction for 12h, filtering, and drying at 110 ℃ for 10h to obtain a catalyst precursor;
(2) calcining the catalyst precursor obtained in the step (1) at 800 ℃ for 3h to obtain the catalystAgent Co0.5/Fe2O3-CaO；
Example 5
A preparation method of a biodiesel magnetic solid base catalyst comprises the following steps:
1) adding CaCl2And FeCl3·6H2O salt solution in a ratio of 1: 1, adding CoSO4·7H2O, wherein the molar ratio of Co to Ca is 0.6:1, dropwise adding a sodium hydroxide solution to form a colloid after stirring and dissolving, continuously stirring for 60min, transferring to a reaction kettle, heating to 180 ℃ for hydrothermal reaction for 13h, filtering, and drying at 120 ℃ for 6h to obtain a catalyst precursor;
(2) calcining the catalyst precursor obtained in the step (1) at 900 ℃ for 4h to obtain a catalyst Co0.6/Fe2O3-CaO；
| The molar ratio of Co to Ca is: 0.2:1 to 0.6:1 | Calcination temperature | |
| Example 1 | 0.2:1 | 500℃ |
| Example 2 | 0.4:1 | 600℃ |
| Example 3 | 0.45:1 | 700℃ |
| Example 4 | 0.5:1 | 800℃ |
| Example 5 | 0.6:1 | 900℃ |
And (3) performance testing:
(1) FIG. 1 shows examples 2, 3 and 4 and Fe without Co doping2O3CaO catalyst and Fe2O3And the XRD test pattern of CaO standard PDF card shows that the transition metal element Co is doped into the mixed metal oxide Fe2O3Co doping into CaO on CaO, causing the CaO lattice to deform and the crystal diffraction peaks to shift slightly to higher angles; in addition, Co is doped into Fe2O3In such a way that part of Fe2O3Is transformed from alpha-Fe2O3Conversion to gamma-Fe2O3；
(2) FIG. 2 shows examples 2, 3 and 4 and Fe without Co doping2O3VSM test chart of-CaO catalyst, the result shows that Co doping enters Fe2O3The catalyst has magnetism, and the magnetic strength changes along with the change of the doping amount;
(3) FIG. 3 is an SEM image of the catalyst prepared in example 3, and the analysis result shows that the particles of the catalyst are below 100 nm.
(4) FIG. 4 is NH of the catalyst prepared in example 33TPD and CO2TPD plot, NH3And CO2The appearance of desorption peaks shows that the catalyst has two catalysis characteristics of Lewis acid and alkali.
The acid-base bifunctional magnetic nano-catalyst prepared in examples 1-5 catalyzes the transesterification reaction of vegetable oil and methanol.
Vegetable oils (soybean oil and palm)Oil) and methanol, the reaction was carried out in a three-necked flask equipped with a reflux condenser and mechanical stirring, 11.3g of soybean oil and 6.5g of methanol were added according to the alcohol-oil molar ratio of 15:1, and 3 wt% of a catalyst (three sets of experiments under the same conditions, except that the catalysts added were prepared as in examples 1 to 3, respectively, were heated in an electric stirrer and a water bath to 70 deg.c, and as a comparison, two sets of comparative experiments were set up, and the same amount of Fe not doped with Co was added2O3and-CaO and pure CaO), maintaining the rotation speed of 300-600 r/min, keeping the condensation reflux reaction for 2.5h, separating the catalyst by using an external magnetic field, standing and layering, taking the upper layer as biodiesel and the lower layer as glycerol, diluting the upper layer liquid by using n-hexane for a certain concentration, and analyzing and determining by adopting GC-MS.
As can be seen from test examples 1 and 2, the molar ratio of Co to Ca was 0.2:1, calcining at 500 ℃ for 1h, wherein the molar ratio of the catalyst precursor to Co to Ca is 0.4:1, calcination at 600 ℃ for 2h of the catalyst prepared may be Ca (OH)2The decomposition is not thorough, the catalytic activity is relatively low, and the yield of the biodiesel is low;
as can be seen from test example 3, the molar ratio of Co to Ca was 0.45: 1, the catalyst prepared by calcining the catalyst precursor for 2 hours at 700 ℃ has the strongest acid-base active site synergistic effect and the highest catalytic activity, so that higher biodiesel yield can be obtained;
as can be seen from test examples 4 and 5, the molar ratio of Co to Ca was 0.5:1, calcining at 800 ℃ for 3h, wherein the molar ratio of the catalyst precursor to Co to Ca is 0.6:1, calcining the catalyst precursor for 4h at 900 ℃, and the catalytic activity of the catalyst is difficult to increase, probably when the molar ratio of Co to Ca is 0.45: under the condition of 1, the synergistic effect of acid-base active sites reaches balance, and the catalytic activity reaches the strongest, so that the catalytic activity is basically unchanged by adding the molar ratio of Co.
As comparative examples, CaCl was used in the same molar ratios as in examples 1 to 52And FeCl3·6H2Solution of O salt, preparation of Fe2O3CaO, and both it and pure CaO were used in the transesterification of soybean oil and palm oil with methanol, as can be seen from Table 2, Fe without Co doping using the same transesterification conditions2O3The yield of biodiesel prepared by catalyzing soybean oil and palm oil by CaO and pure CaO is higher than that of Fe doped with Co2O3Low CaO, indicating pure CaO and Fe without Co doping2O3CaO has a catalytic activity lower than that of Co-doped Fe2O3-CaO。
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. An acid-base bifunctional magnetic nano catalyst for biodiesel, which is characterized by having a structure of Co/Fe2O3-CaO; wherein the molar ratio of Co to Ca is 0.2: 1-0.6: 1.
2. The catalyst of claim 1, wherein the molar ratio of Co to Ca is 0.4:1 to 0.5: 1.
3. A preparation method of a biodiesel acid-base bifunctional magnetic nano catalyst is characterized by comprising the following steps:
1) adding CaCl2And FeCl3·6H2O salt solution in a ratio of 1: 1, adding CoSO4·7H2O, wherein the molar ratio of Co to Ca is 0.2: 1-0.6: 1, dissolving, then dropwise adding a NaOH solution to form a colloid, continuously stirring for 20-60 min, transferring to a reaction kettle, heating to 180 ℃, carrying out hydrothermal reaction for 9-13 h, filtering, and drying at 60-120 ℃ for 6-24 h to obtain a catalyst precursor;
2) calcining the catalyst precursor obtained in the step (1) at 500-900 ℃ for 1-4 h to obtain a catalyst Co/Fe2O3-CaO。
4. The method according to claim 3, wherein the molar ratio of Co to Ca is 0.4:1 to 0.5: 1.
5. The process as claimed in claim 3, wherein CoSO is added in step 1)4·7H2And continuously stirring for 30-50 min after the O is stirred and dissolved.
6. The method as claimed in claim 3, wherein the hydrothermal reaction in step 1) is carried out for 10-12 h.
7. The method as set forth in claim 3, wherein the catalyst precursor is obtained by drying at 90 to 110 ℃ for 10 to 12 hours in the step 1).
8. The method as set forth in claim 3, wherein the Co/Fe catalyst is obtained by calcining at 600-800 ℃ for 1-3 h in the step 2)2O3-CaO。
9. The application of the acid-base bifunctional magnetic nano catalyst for biodiesel according to claim 1 or 2 in the preparation of biodiesel.
10. The method is characterized in that the biodiesel is prepared by performing ester exchange reaction on methanol and vegetable oil, wherein the molar ratio of the methanol to the vegetable oil is 12: 1-18: 1; the heating method is heating in water bath to 60-80 ℃; the adding amount of the catalyst is 2-4% of the mass of the vegetable oil; the heating time is 90-150 min.
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