CN113275015B - 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 PDF

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CN113275015B
CN113275015B CN202110572793.4A CN202110572793A CN113275015B CN 113275015 B CN113275015 B CN 113275015B CN 202110572793 A CN202110572793 A CN 202110572793A CN 113275015 B CN113275015 B CN 113275015B
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cao
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陈冠益
夏晒歌
李婉晴
颜蓓蓓
程占军
林法伟
李丽萍
杜桂月
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Tianjin University
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C—CHEMISTRY; METALLURGY
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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 method 2 O 3 Mixing CaO, co is doped into CaO, so that Ca 2+ Increased stability, fe 2 O 3 For Ca 2+ Also has certain stabilizing effect, and the two simultaneously relieve Ca 2+ The loss of the catalyst improves the catalytic activity and the service life of the catalyst. And the incorporation of Co results in Fe 2 O 3 From alpha-Fe 2 O 3 Conversion to gamma-Fe 2 O 3 Thereby 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

Biodiesel acid-base bifunctional magnetic nano catalyst, and preparation method and application thereof
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/Fe 2 O 3 A 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 synthesized by ester exchange reaction of renewable resources such as animal and vegetable oil, waste cooking oil, microalgae and the like by using homogeneous or heterogeneous catalysts. Transesterification of homogeneous catalysts is the most common and most commercialized 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.
CaO is widely applied to the catalytic preparation of biodiesel due to the advantages of easily available raw materials, wide sources, low cost, high catalytic activity and the like. 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 problem that the active component of the pure CaO serving as the catalyst is easy to beIn the problems of loss, difficult separation and the like, the invention dopes the transition metal element Co into the mixed metal oxide Fe 2 O 3 Doping Co into CaO on CaO, causing the CaO lattice to deform, ca 2+ Increased stability, and Fe 2 O 3 For Ca 2+ Also has certain stabilizing effect, and the two simultaneously relieve Ca 2+ The loss of the catalyst improves the catalytic activity and the service life of the catalyst. In addition, co is doped into Fe 2 O 3 In (1), make Fe 2 O 3 Is transformed from alpha-Fe 2 O 3 Conversion to gamma-Fe 2 O 3 And 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/Fe 2 O 3 -CaO; wherein the molar ratio of Co to Ca is 0.2.
The molar ratio of Co to Ca is preferably 0.4.
A preparation method of a biodiesel acid-base bifunctional magnetic nano catalyst comprises the following steps:
1) Adding CaCl 2 And FeCl 3 ·6H 2 O salt solution in a ratio of 1:1, adding CoSO 4 ·7H 2 O, wherein the molar ratio of Co to Ca is 0.2;
2) Calcining the catalyst precursor obtained in the step (1) at 500-900 ℃ for 1-4 h to obtain the catalyst Co/Fe 2 O 3 -CaO。
The molar ratio of Co to Ca is preferably 0.4.
The method preferably comprises the step 1) of adding CoSO 4 ·7H 2 And 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 h.
The method preferably comprises the step 1) of drying at 90-110 ℃ for 10-12 h to obtain the catalyst precursor.
The method preferably comprises the step 2) of calcining at 600-800 ℃ for 1-3 h to obtain the catalyst Co/Fe 2 O 3 -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 12-18; the heating method is heating to 60-80 ℃ in water bath; the adding amount of the catalyst is 2-4% of the weight 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 Fe 2 O 3 In 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 an excellent biodiesel catalyst;
(2) The invention dopes Co element into Fe 2 O 3 In the middle, make Fe 2 O 3 Is transformed from alpha-Fe 2 O 3 Conversion to gamma-Fe 2 O 3 The 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 method 2 O 3 And CaO, caO having basic active sites, fe 2 O 3 Has acid active sites, co is doped into CaO to deform CaO crystal lattice, and Ca 2+ Increased stability, in addition to Fe 2 O 3 For Ca 2+ Also has certain stabilizing effect, and the two simultaneously relieve Ca 2+ The loss of the catalyst improves the catalytic activity and the service life of the catalyst. And the incorporation of Co results in Fe 2 O 3 From alpha-Fe 2 O 3 Conversion to gamma-Fe 2 O 3 Therefore, 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 soybean oil to be converted into biodiesel, the yield of the biodiesel can reach 98.0% under the optimal preparation and implementation conditions, and the yield is higher than that of Fe under the same reaction conditions 2 O 3 -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 doping 2 O 3 CaO catalyst and Fe 2 O 3 And XRD test pattern of CaO standard PDF card;
FIG. 2 shows examples 2, 3 and 4 and Fe without Co doping 2 O 3 -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 invention 3 TPD and CO 2 -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 CaCl 2 And FeCl 3 ·6H 2 O salt solution in a ratio of 1:1, adding CoSO 4 ·7H 2 O, 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 ℃ to perform 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 Co 0.2 /Fe 2 O 3 -CaO；
Example 2
A preparation method of a biodiesel magnetic solid base catalyst comprises the following steps:
1) Adding CaCl 2 And FeCl 3 ·6H 2 O salt solution in a ratio of 1:1, adding CoSO 4 ·7H 2 O, 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 Co 0.4 /Fe 2 O 3 -CaO；
Example 3
A preparation method of a biodiesel magnetic solid base catalyst comprises the following steps:
(1) Adding CaCl 2 And FeCl 3 ·6H 2 O salt solution 1:1, adding CoSO 4 ·7H 2 O, wherein the molar ratio of Co to Ca is 0.45:1, stirring and dissolving, and then dropwise adding sodium hydroxide solution to formContinuously stirring the colloid for 40min, transferring the colloid into 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 Co 0.45 /Fe 2 O 3 -CaO；
Example 4
A preparation method of a biodiesel magnetic solid base catalyst comprises the following steps:
1) Adding CaCl 2 And FeCl 3 ·6H 2 O salt solution in a ratio of 1:1, adding CoSO 4 ·7H 2 O, 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 ℃ to perform 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 a catalyst Co 0.5 /Fe 2 O 3 -CaO；
Example 5
A preparation method of a biodiesel magnetic solid base catalyst comprises the following steps:
1) Adding CaCl 2 And FeCl 3 ·6H 2 O salt solution in a ratio of 1:1, adding CoSO 4 ·7H 2 O, 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 Co 0.6 /Fe 2 O 3 -CaO；
The molar ratio of Co to Ca is: 0.2 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 doping 2 O 3 CaO catalyst and Fe 2 O 3 And the XRD test pattern of CaO standard PDF card shows that the transition metal element Co is doped into the mixed metal oxide Fe 2 O 3 Co 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 Fe 2 O 3 In such a way that part of Fe 2 O 3 Is transformed from alpha-Fe 2 O 3 Conversion to gamma-Fe 2 O 3 ；
(2) FIG. 2 shows examples 2, 3 and 4 and Fe without Co doping 2 O 3 VSM test chart of-CaO catalyst, the result shows that Co doping enters Fe 2 O 3 The 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 3 3 TPD and CO 2 TPD plot, NH 3 And CO 2 The 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.
Transesterification of vegetable oils (soybean oil and palm oil) with methanol was carried out in a three-necked flask equipped with reflux condenser and mechanical stirring, 11.3g of soybean oil and 6.5g of methanol were added according to the molar ratio of methanol to oil 15 in 1, and 3wt% of catalyst (three sets of tests under the same conditions, except that the added catalysts were prepared in examples 1 to 3, respectively, were added after heating in a water bath to 70 ℃ by electric stirring, and two sets of comparative experiments were set for comparison, and the same amount of Fe not doped with Co was added 2 O 3 -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.
Figure BDA0003083323060000061
As can be seen from test examples 1 and 2, the molar ratio of Co to Ca was 0.2:1, calcining the catalyst precursor for 1h at 500 DEG CAnd the molar ratio of Co and Ca was 0.4:1, calcination at 600 ℃ for 2h produces a catalyst that may be Ca (OH) 2 The 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 0.45:1, the acid-base active site synergy reaches balance, and the catalytic activity reaches the strongest, so that the catalytic activity is basically unchanged by adding the Co molar ratio.
As comparative examples, caCl was used in the same molar ratios as in examples 1 to 5 2 And FeCl 3 ·6H 2 Solution of O salt, preparation of Fe 2 O 3 CaO, 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 conditions 2 O 3 The yield of biodiesel prepared by catalyzing soybean oil and palm oil by CaO and pure CaO is higher than that of Fe doped with Co 2 O 3 Low CaO, indicating pure CaO and Fe without Co doping 2 O 3 CaO has a catalytic activity lower than that of Co-doped Fe 2 O 3 -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 (7)

1. An application of a biodiesel acid-base bifunctional magnetic nano catalyst in biodiesel preparation is characterized in that the structure is Co/Fe 2 O 3 -CaO; wherein the molar ratio of Co to Ca is 0.2; the preparation method comprises the following steps:
1) Adding CaCl 2 And FeCl 3 ·6H 2 O salt solution in a ratio of 1:1, adding CoSO 4 ·7H 2 O, wherein the molar ratio of Co to Ca is 0.2;
2) Calcining the catalyst precursor obtained in the step (1) at 500-900 ℃ for 1-4 h to obtain the catalyst Co/Fe 2 O 3 -CaO。
2. Use according to claim 1, wherein the molar ratio of Co to Ca is from 0.4.
3. Use according to claim 1, characterized in that in step 1) CoSO is added 4 ·7H 2 And continuously stirring for 30-50 min after the O is stirred and dissolved.
4. The method as claimed in claim 1, wherein the hydrothermal reaction in step 1) is carried out for 10 to 12 hours.
5. The use of claim 1, wherein the catalyst precursor is obtained by drying at 90-110 ℃ for 10-12 h in step 1).
6. The method as set forth in claim 1, wherein the Co/Fe catalyst is obtained by calcining at 600-800 ℃ for 1-3 h in step 2) 2 O 3 -CaO。
7. 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; the heating method is heating to 60-80 ℃ in water bath; the adding amount of the catalyst is 2-4% of the weight of the vegetable oil; the heating time is 90-150 min.
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