CN111715281A - Catalyst for producing green diesel oil additive and preparation method thereof - Google Patents

Catalyst for producing green diesel oil additive and preparation method thereof Download PDF

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CN111715281A
CN111715281A CN202010633218.6A CN202010633218A CN111715281A CN 111715281 A CN111715281 A CN 111715281A CN 202010633218 A CN202010633218 A CN 202010633218A CN 111715281 A CN111715281 A CN 111715281A
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cerium
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teaps
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ionic liquid
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闫英辉
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
    • B01J31/0279—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the cationic portion being acyclic or nitrogen being a substituent on a ring
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
    • B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
    • B01J31/0294—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate by polar or ionic interaction with the substrate, e.g. glass
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0298—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature the ionic liquids being characterised by the counter-anions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48—Preparation of compounds having groups
    • C07C41/50—Preparation of compounds having groups by reactions producing groups
    • C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones

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Abstract

The invention discloses a catalyst for producing green diesel oil additive and a preparation method thereof, which comprises the steps of preparing zirconium-cerium composite oxide and MoO3/ZrO2‑CeO2Preparing solid super acid, preparing a ionic liquid precursor TEAPS, and carrying out in-situ loading on cerium-based solid ionic liquid to obtain the cerium-based solid ionic liquid; the catalyst is prepared by MoO3/ZrO2‑CeO2Composite catalyst combining solid super acid and cerium-based solid ionic liquid, and MoO in composite catalyst3/ZrO2‑CeO2The mass fraction of the solid super acid is 60-90 wt%. The composite catalyst of the invention can solve the problems of difficult separation of the catalyst and the product and the capacity of the reaction active componentThe catalyst can be kept in a solid state, and the catalyst has moderate acid amount and acid strength so as to be non-corrosive to a reactor, and has high catalytic efficiency and good selectivity of the obtained main product.

Description

Catalyst for producing green diesel oil additive and preparation method thereof
Technical Field
The invention belongs to the technical field of petrochemical industry, relates to a diesel additive technology, and particularly relates to a catalyst for producing a green diesel additive and a preparation method thereof.
Background
With the wide application of diesel oil, the demand of international society for diesel oil is increasing year by year, and the problem of harmful substance emission is getting more serious, which seriously affects the sustainable development of human society. Therefore, the problems that the combustion efficiency of the diesel oil is effectively improved and the emission of harmful substances is reduced are urgently needed to be solved by people at present.
In order to meet the social demand of developing high-efficiency and clean diesel, researchers in various countries increase the research strength of diesel additives. On the premise of maintaining the normal operation of an engine, the diesel additive can enable combustion to be more complete by changing the property of fuel, thereby playing an important role in reducing energy consumption and emission. In addition, the diesel additive is used without changing the structure of the engine, and has certain economic advantages. The cetane number improver can effectively improve the antiknock property and the combustibility of diesel oil, so that the cetane number improver shows obvious superiority in the aspects of reducing oil consumption, emission, improving the cold starting performance of an engine, reducing noise and the like.
Polyoxymethylene dimethyl ether as diesel additive is a general name of a class of substances and has a molecular formula of CH3(CH2O)nCH3Wherein n is 2-11, they have high cetane number (average up to 76) and high oxygen content (45-49%), and good intersolubility with diesel oil, and are suitable for being used as oil additive, and polyformaldehyde dimethyl ether (DMM) with n being more than or equal to 3 and less than or equal to 83-8) The blending quality of the diesel oil is higher than that of ultra-low sulfur diesel oil, 10 to 30 percent of NO can be greatly reduced by adding the diesel oilxAnd the emission of CO and smoke dust, the tail gas pollution is reduced by more than 50 percent, and the lubricity of the diesel oil can be remarkably improved, so the diesel oil additive is considered to be an environment-friendly diesel oil additive with great application prospect.
BASF corporation (WO 2006/045506A 1) uses sulfuric acid and trifluoromethanesulfonic acid as catalysts, and methanol, methylal, trioxymethylene, paraformaldehyde and the like as raw materials to obtain PODE1-10 products. PODE Synthesis Using liquid acid as catalyst3-8But the cost is low, but the product is extremely unfavorable for separation because the catalyst has strong corrosion to equipment and is in the same phase with the product after the reaction is finished.
Chinese patent CN101182367A adopts ionic liquid to catalyze methanol and trioxymethylene to react to synthesize polyoxymethylene dimethyl ether, wherein the cation part of the ionic liquid is selected from one of imidazole cation, pyridine cation, quaternary ammonium salt cation and quaternary phosphonium salt cation, the anion part is selected from one of p-methyl benzene sulfonate, trifluoromethyl sulfonate, methyl sulfonate, hydrogen sulfate and trifluoroacetate, the reaction conversion rate can reach 90.3 percent at most, and PODE (peroxidase)3-8The selectivity can reach 42.6%. However, the ionic liquid is in liquid form, and the subsequent separation caused by high cost and relative complex separationThe energy consumption of the separation operation is high.
At present, the preparation process of polyoxymethylene dimethyl ether has a plurality of technical defects of common catalysts such as: the inorganic acid catalyst is easy to corrode equipment, the ionic liquid catalyst is not easy to recycle, and the selectivity of reaction products is poor. Meanwhile, too high acid strength of the catalyst and too much strong acid amount easily cause a large amount of methyl formate to be generated in the reaction, so that the selectivity of the target product is reduced.
Disclosure of Invention
In order to solve the defects of poor catalyst stability, difficult cyclic utilization, corrosive catalyst to reaction equipment and low selectivity of polyoxymethylene dimethyl ether in the prior art of diesel additives, the invention discloses a catalyst for producing a green diesel additive and a preparation method thereof, wherein the catalyst is MoO3/ZrO2-CeO2The composite catalyst combines solid super acid and cerium-base solid ionic liquid. The composite catalyst can solve the problems that the catalyst is difficult to separate from the product and the stability is poor due to the easy loss of reaction active components, and has no corrosion to a reactor because the catalyst can keep a solid state and the acid amount and the acid strength of the catalyst are relatively moderate, the catalytic efficiency is high and the selectivity of the obtained main product is good.
The invention is realized by the following technical scheme:
in one aspect, the invention discloses a catalyst for producing green diesel additive, which is prepared from MoO3/ZrO2-CeO2The MoO is a composite catalyst formed by combining solid super acid with cerium-based solid ionic liquid3/ZrO2-CeO2The solid superacid is a zirconium-cerium composite oxide loaded MoO with a mesoporous structure3Synthesized, the cerium-based solid ionic liquid is Ce0.33[TEAPS]2PMo12O40、Ce0.66[TEAPS]PMo12O40、Ce0.33[TEAPS]HPMo12O40In the composite catalyst, MoO3/ZrO2-CeO2The mass fraction of the solid super acid is 60-90 wt%.
On the other hand, the invention also discloses a preparation method of the catalyst for producing the green diesel additive, which is realized by the following specific steps:
(1) preparation of zirconium cerium composite oxide
Mixing and stirring a zirconyl nitrate solution and a cerium nitrate solution for 25-35 min, adding urea and PVA, continuously stirring for 25-35 min, reacting at 80-90 ℃ for 12-24 h, centrifuging, washing and drying the obtained product, and roasting at 500-700 ℃ for 5-7 h to obtain a zirconium-cerium composite oxide; the mass ratio of zirconium to cerium is 1: 2-2: 1, the addition amount of the urea is 10-20 times of the sum of the amounts of zirconyl nitrate and cerium nitrate, and the addition amount of the PVP is 2-4 wt% of the total weight of the zirconyl nitrate and the cerium nitrate; preferably, the mass concentration of the zirconyl nitrate solution is 0.2-0.4 mol/L, and the mass concentration of the cerium nitrate solution is 0.2-0.4 mol/L;
(2) preparation of solid superacid
Firstly, ultrasonically dispersing zirconium-cerium composite oxide into deionized water, then adding ammonium molybdate into the deionized water, evaporating the ammonium molybdate to dryness in a water bath condition at the temperature of 90 ℃, roasting the evaporated material for 4-6 hours at the temperature of 500-800 ℃ to obtain MoO3MoO in an amount of 15 to 30 wt%3/ZrO2-CeO2Solid super acid;
(3) preparation of ionic liquid precursor TEAPS
Adding 1, 3-propane sultone and cyclohexane into an ultrasonic reactor, stirring and dissolving, then introducing argon for 30min, opening the ultrasonic reactor, keeping the power at 100-200W, then dropwise adding triethylamine into the reactor, reacting for 4-6 h to obtain a mixture, and then centrifuging, washing and drying the mixture to obtain a white powder solid, namely an ionic liquid precursor, which is marked as TEAPS; wherein the mass ratio of triethylamine to 1, 3-propane sultone is 1:1, the mass concentration of 1, 3-propane sultone in cyclohexane is 0.1 mol/L;
(4) in-situ loading of cerium-based solid ionic liquids
Adding MoO3/ZrO2-CeO2Adding solid super acid, phosphomolybdic acid, cerium nitrate and TEAPS intoDeionized water
Stirring the mixture at room temperature for 15min, transferring the mixture into an ultrasonic reactor, reacting the mixture for 4-6 h at 100-300W, and then sequentially centrifuging, washing and drying the mixture to obtain a composite catalyst of solid superacid and cerium-based solid ionic liquid; the cerium-based solid ionic liquid synthesized in the reaction process of phosphomolybdic acid, cerium nitrate and TEAPS is Ce0.33[TEAPS]2PMo12O40、Ce0.66[TEAPS]PMo12O40、Ce0.33[TEAPS]HPMo12O40One kind of (1).
In a preferred embodiment, in the step (4), the ratio of the amounts of TEAPS and phosphomolybdic acid is (1-2): 1, the ratio of the amounts of cerium nitrate and phosphomolybdic acid is (0.33-0.66): 1, and MoO in the composite catalyst3/ZrO2-CeO2The mass fraction of the solid superacid is 70-90 wt%.
Compared with the prior art, the invention has the following beneficial effects.
1) On one hand, compared with the conventional liquid ionic liquid, the cerium-based solid ionic liquid can be effectively separated from a product, and active components are not easy to lose, so that the cerium-based solid ionic liquid is beneficial to cyclic utilization; on the other hand, the ion liquid takes heteropoly acid radicals with multi-charge characteristics as anions, simultaneously takes organic cations, metal cations and protons as counter ions, constructs heteropoly acid functional ion liquid organic-inorganic hybrid materials with cation parts having Br nano-Lewis dual acidity, and introduces strong acid functional groups, organic cations and metal cations into the organic cations to replace counter protons to form acid salts, so that the acid strength of the organic cations is enhanced, and higher catalytic activity and reaction stability are embodied in the reaction process.
2) The cerium-based solid ionic liquid can form a unique microenvironment on the surface of the composite catalyst, which not only can effectively avoid the inhibition of byproducts on catalytic active points in the reaction process, but also can strengthen the cerium-based solid ionic liquid and the solid super acidic MoO3/ZrO2-CeO2In the middle of the cooperationThe same effect is achieved. Meanwhile, the existence of various types of acidic sites in the composite catalyst can prevent the reduction of the reaction performance of the catalyst caused by the inactivation of catalytic active sites of the same type.
3) Cerium-based solid ionic liquid and MoO3/ZrO2-CeO2The mesoporous structure of the carrier of the composite catalyst formed by the solid superacid can form a geometric confinement for the active components, thereby effectively preventing the excessive polymerization of the polyoxymethylene dimethyl ether and improving the selectivity of a target product. In addition, the cerium-based solid ionic liquid has relatively weaker acid strength and MoO (MoO) compared with the conventional multi-sulfonate acidic ionic liquid3/ZrO2-CeO2Compared with the conventional solid super acid, the active component is not easy to lose, and the acid strength is relatively weak. Therefore, the composite catalyst is not easy to generate a large amount of by-product methyl formate in the reaction process, so that the selectivity of the main product polyoxymethylene dimethyl ether is enhanced.
4) SO on cerium-based solid Ionic liquids4 2-With solid super acidic MoO3/ZrO2-CeO2ZrO of2-CeO2Can interact with each other to form a new reactive site SO4 2-/ZrO2-CeO2The solid super acid can strengthen the synergistic effect between the solid ionic liquid and the carrier, and further strengthen the catalytic reaction activity.
Detailed Description
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art.
Example 1
A preparation method of a catalyst for producing a green diesel additive is realized by the following specific steps:
(1) preparation of zirconium cerium composite oxide
Mixing and stirring 0.2mol/L zirconyl nitrate solution and 0.4mol/L cerous nitrate solution for 25min, then adding urea and PVA, continuing stirring for 25min, reacting for 24h at 80 ℃, centrifuging, washing and drying the obtained product, and roasting for 7 h at 500 ℃ to obtain zirconium-cerium composite oxide; the mass ratio of zirconium to cerium is 1:2, the addition amount of the urea is 10 times of the sum of the mass amounts of the zirconyl nitrate and the cerium nitrate, and the addition amount of the PVP is 2wt% of the total weight of the zirconyl nitrate and the cerium nitrate;
(2) preparation of solid superacid
Firstly, ultrasonically dispersing zirconium-cerium composite oxide into deionized water, then adding ammonium molybdate into the deionized water, evaporating the mixture to dryness under the condition of 90 ℃ water bath, roasting the evaporated material at 500 ℃ for 6 hours to obtain MoO3MoO in an amount of 15 wt%3/ZrO2-CeO2Solid super acid;
(3) preparation of ionic liquid precursor TEAPS
Adding 1, 3-propane sultone and cyclohexane into an ultrasonic reactor, stirring and dissolving, then introducing argon for 30min, opening the ultrasonic reactor, keeping the power at 100W, then dropwise adding triethylamine into the reactor, reacting for 4h to obtain a mixture, and then centrifuging, washing and drying the mixture to obtain a white powder solid, namely an ionic liquid precursor, which is marked as TEAPS; wherein the mass ratio of triethylamine to 1, 3-propane sultone is 1:1, the mass concentration of 1, 3-propane sultone in cyclohexane is 0.1 mol/L;
(4) in-situ loading of cerium-based solid ionic liquids
Adding MoO3/ZrO2-CeO2Adding solid superacid, phosphomolybdic acid, cerium nitrate and TEAPS into deionized water
Stirring the mixture at room temperature for 15min, transferring the mixture into an ultrasonic reactor, reacting the mixture for 6h at 100W, and then sequentially centrifuging, washing and drying the mixture to obtain the composite catalyst of the solid superacid and the cerium-based solid ionic liquid; the mass ratio of TEAPS to phosphomolybdic acid is 2:1, the mass ratio of cerium nitrate to phosphomolybdic acid is 0.33:1, and MoO in the composite catalyst3/ZrO2-CeO2The mass fraction of the solid super acid is 70 wt%; the cerium-based solid ionic liquid synthesized in the reaction process of phosphomolybdic acid, cerium nitrate and TEAPS is Ce0.33[TEAPS]2PMo12O40The resulting catalyst was labeled catalyst A.
Adding 19.2 g of methanol, 54.0g of trioxymethylene and 4.0g of catalyst B into a 100mL high-pressure reaction kettle respectively, and filling N2Heating to the pressure of 2.5MPa, slowly heating to 200 ℃, and stirring for reaction for 10 hours. The reaction product was cooled to room temperature, and the yield of PODE3-8 by gas chromatography was 48.6%, and the conversion of methanol was 98.3%.
Example 2
A preparation method of a catalyst for producing a green diesel additive is realized by the following specific steps:
(1) preparation of zirconium cerium composite oxide
Mixing and stirring 0.4mol/L zirconyl nitrate solution and 0.2mol/L cerous nitrate solution for 35min, then adding urea and PVA, continuing stirring for 35min, reacting at 90 ℃ for 12h, centrifuging, washing and drying the obtained product, and roasting at 700 ℃ for 5h to obtain zirconium-cerium composite oxide; the mass ratio of zirconium to cerium is 2:1, the addition amount of the urea is 20 times of the sum of the mass amounts of the zirconyl nitrate and the cerium nitrate, and the addition amount of the PVP is 4wt% of the total weight of the zirconyl nitrate and the cerium nitrate;
(2) preparation of solid superacid
Firstly, ultrasonically dispersing zirconium-cerium composite oxide into deionized water, then adding ammonium molybdate into the deionized water, evaporating the mixture to dryness under the condition of 90 ℃ water bath, roasting the evaporated material at 800 ℃ for 4 hours to obtain MoO3MoO in an amount of 30 wt%3/ZrO2-CeO2Solid super acid;
(3) preparation of ionic liquid precursor TEAPS
Adding 1, 3-propane sultone and cyclohexane into an ultrasonic reactor, stirring and dissolving, then introducing argon for 30min, opening the ultrasonic reactor, keeping the power at 200W, then dropwise adding triethylamine into the reactor, reacting for 4h to obtain a mixture, and then centrifuging, washing and drying the mixture to obtain a white powder solid, namely an ionic liquid precursor, which is marked as TEAPS; wherein the mass ratio of triethylamine to 1, 3-propane sultone is 1:1, the mass concentration of 1, 3-propane sultone in cyclohexane is 0.1 mol/L;
(4) in-situ loading of cerium-based solid ionic liquids
Adding MoO3/ZrO2-CeO2Adding solid superacid, phosphomolybdic acid, cerium nitrate and TEAPS into deionized water
Obtaining a mixture in water, stirring for 15min at room temperature, transferring the mixture into an ultrasonic reactor, reacting for 4h at 300W, and then sequentially centrifuging, washing and drying to obtain the composite catalyst of the solid superacid and the cerium-based solid ionic liquid; the mass ratio of TEAPS to phosphomolybdic acid is 1:1, the mass ratio of cerium nitrate to phosphomolybdic acid is 0.66:1, and MoO in the composite catalyst3/ZrO2-CeO2The mass fraction of the solid super acid is 90 wt%; the cerium-based solid ionic liquid synthesized in the reaction process of phosphomolybdic acid, cerium nitrate and TEAPS is Ce0.66[TEAPS]PMo12O40The resulting catalyst was labeled catalyst B.
Adding 19.2 g of methanol, 54.0g of trioxymethylene and 4.0g of catalyst A into a 100mL high-pressure reaction kettle respectively, and filling N2Heating to the pressure of 2.5MPa, slowly heating to 200 ℃, and stirring for reaction for 10 hours. The reaction product was cooled to room temperature, and the yield of PODE3-8 was 54.8% by gas chromatography and the conversion of methanol was 99.2%.
Example 3
A preparation method of a catalyst for producing a green diesel additive is realized by the following specific steps:
(1) preparation of zirconium cerium composite oxide
Mixing and stirring 0.2mol/L zirconyl nitrate solution and 0.2mol/L cerous nitrate solution for 30min, then adding urea and PVA, continuing stirring for 30min, reacting at 85 ℃ for 18h, centrifuging, washing and drying the obtained product, and roasting at 650 ℃ for 5h to obtain zirconium-cerium composite oxide; the mass ratio of zirconium to cerium is 1:1, the addition amount of the urea is 15 times of the sum of the mass amounts of the zirconyl nitrate and the cerium nitrate, and the addition amount of the PVP is 3wt% of the total weight of the zirconyl nitrate and the cerium nitrate;
(2) preparation of solid superacid
Firstly, ultrasonically dispersing zirconium-cerium composite oxide into deionized water, then adding ammonium molybdate into the deionized water, evaporating the mixture to dryness under the condition of 90 ℃ water bath, and roasting the evaporated material at 650 ℃ for 5 hours to obtain MoO3MoO in an amount of 24 wt%3/ZrO2-CeO2Solid super acid;
(3) preparation of ionic liquid precursor TEAPS
Adding 1, 3-propane sultone and cyclohexane into an ultrasonic reactor, stirring and dissolving, then introducing argon for 30min, opening the ultrasonic reactor, keeping the power at 150W, then dropwise adding triethylamine into the reactor, reacting for 5h to obtain a mixture, and then centrifuging, washing and drying the mixture to obtain a white powder solid, namely an ionic liquid precursor, which is marked as TEAPS; wherein the mass ratio of triethylamine to 1, 3-propane sultone is 1:1, the mass concentration of 1, 3-propane sultone in cyclohexane is 0.1 mol/L;
(4) in-situ loading of cerium-based solid ionic liquids
Adding MoO3/ZrO2-CeO2Adding solid superacid, phosphomolybdic acid, cerium nitrate and TEAPS into deionized water
Stirring the mixture at room temperature for 15min, transferring the mixture into an ultrasonic reactor, reacting the mixture for 5h at 200W, and then sequentially centrifuging, washing and drying the mixture to obtain the composite catalyst of the solid superacid and the cerium-based solid ionic liquid; the mass ratio of TEAPS to phosphomolybdic acid is 1:1, the mass ratio of cerium nitrate to phosphomolybdic acid is 0.33:1, and MoO in the composite catalyst3/ZrO2-CeO2The mass fraction of the solid super acid is 80 wt%; the cerium-based solid ionic liquid synthesized in the reaction process of phosphomolybdic acid, cerium nitrate and TEAPS is Ce0.33[TEAPS]HPMo12O40The resulting catalyst was labeled catalyst C.
Adding 19.2 g of methanol, 54.0g of trioxymethylene and 4.0g of catalyst C into a 100mL high-pressure reaction kettle respectively, and filling N2Heating to the pressure of 2.5MPa, slowly heating to 200 ℃, and stirring for reaction for 10 hours. The reaction product was cooled to room temperature, and the yield of PODE3-8 by gas chromatography was 51.8%, conversion of methanolThe conversion rate was 99.5%.
Comparative example 1
(1) Preparation of zirconium cerium composite oxide
Mixing and stirring 0.2mol/L zirconyl nitrate solution and 0.2mol/L cerous nitrate solution for 30min, then adding urea and PVA, continuing stirring for 30min, reacting at 85 ℃ for 18h, centrifuging, washing and drying the obtained product, and roasting at 650 ℃ for 5h to obtain zirconium-cerium composite oxide; the mass ratio of zirconium to cerium is 1:1, the addition amount of the urea is 15 times of the sum of the mass amounts of the zirconyl nitrate and the cerium nitrate, and the addition amount of the PVP is 3wt% of the total weight of the zirconyl nitrate and the cerium nitrate;
(2) preparation of solid superacid
Firstly, ultrasonically dispersing zirconium-cerium composite oxide into deionized water, then adding ammonium molybdate into the deionized water, evaporating the mixture to dryness under the condition of 90 ℃ water bath, and roasting the evaporated material at 650 ℃ for 5 hours to obtain MoO3MoO in an amount of 24 wt%3/ZrO2-CeO2The solid super acid and the resulting catalyst was labeled catalyst D.
Adding 19.2 g of methanol, 54.0g of trioxymethylene and 4.0g of catalyst D into a 100mL high-pressure reaction kettle respectively, and filling N2Heating to the pressure of 2.5MPa, slowly heating to 200 ℃, and stirring for reaction for 10 hours. The reaction product was cooled to room temperature, and the yield of PODE3-8 by gas chromatography was 31.6%, and the conversion of methanol was 86.7%.
Comparative example 2
(1) Preparation of ionic liquid precursor TEAPS
Adding 1, 3-propane sultone and cyclohexane into an ultrasonic reactor, stirring and dissolving, then introducing argon for 30min, opening the ultrasonic reactor, keeping the power at 150W, then dropwise adding triethylamine into the reactor, reacting for 5h to obtain a mixture, and then centrifuging, washing and drying the mixture to obtain a white powder solid, namely an ionic liquid precursor, which is marked as TEAPS; wherein the mass ratio of triethylamine to 1, 3-propane sultone is 1:1, the mass concentration of 1, 3-propane sultone in cyclohexane is 0.1 mol/L;
(2) preparation of cerium-based solid ionic liquid
Adding phosphomolybdic acid, cerium nitrate and TEAPS into deionized water to obtain a mixture, stirring for 15min at room temperature, transferring the mixture into an ultrasonic reactor, reacting for 5h at 200W, and then sequentially centrifuging, washing and drying to obtain a cerium-based solid ionic liquid; the mass ratio of TEAPS to phosphomolybdic acid is 1:1, the mass ratio of cerium nitrate to phosphomolybdic acid is 0.33:1, and the synthesized cerium-based solid ionic liquid is Ce0.33[TEAPS]HPMo12O40The resulting catalyst was labeled catalyst E.
Adding 19.2 g of methanol, 54.0g of trioxymethylene and 4.0g of catalyst E into a 100mL high-pressure reaction kettle respectively, and filling N2Heating to the pressure of 2.5MPa, slowly heating to 200 ℃, and stirring for reaction for 10 hours. The reaction product was cooled to room temperature, and the yield of PODE3-8 was 44.6% by gas chromatography and the conversion of methanol was 95.3%.
Example 4
Catalyst B was taken for the following cycle test:
adding 19.2 g of methanol, 54.0g of trioxymethylene and 4.0g of catalyst B into a 100mL high-pressure reaction kettle respectively, and filling N2Heating to the pressure of 2.5MPa, slowly heating to 200 ℃, and stirring for reaction for 10 hours. The reaction product was cooled to room temperature, the yield of PODE3-8 and the conversion rate of methanol were analyzed by gas chromatography, the catalyst was directly recycled after centrifugation, and the results obtained after 6 cycles are shown in Table 1 below
Figure 62878DEST_PATH_IMAGE001
。
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (4)

1. A catalyst for producing a green diesel additive, characterized by: is prepared from MoO3/ZrO2-CeO2The MoO is a composite catalyst formed by combining solid super acid with cerium-based solid ionic liquid3/ZrO2-CeO2The solid superacid is a zirconium-cerium composite oxide loaded MoO with a mesoporous structure3Synthesized, the cerium-based solid ionic liquid is Ce0.33[TEAPS]2PMo12O40、Ce0.66[TEAPS]PMo12O40、Ce0.33[TEAPS]HPMo12O40In the composite catalyst, MoO3/ZrO2-CeO2The mass fraction of the solid super acid is 60-90 wt%.
2. A preparation method of a catalyst for producing a green diesel additive is characterized by comprising the following specific steps:
(1) preparation of zirconium cerium composite oxide
Mixing and stirring a zirconyl nitrate solution and a cerium nitrate solution for 25-35 min, adding urea and PVA, continuously stirring for 25-35 min, reacting at 80-90 ℃ for 12-24 h, centrifuging, washing and drying the obtained product, and roasting at 500-700 ℃ for 5-7 h to obtain a zirconium-cerium composite oxide; the mass ratio of zirconium to cerium is 1: 2-2: 1, the addition amount of the urea is 10-20 times of the sum of the amounts of zirconyl nitrate and cerium nitrate, and the addition amount of the PVP is 2-4 wt% of the total weight of the zirconyl nitrate and the cerium nitrate;
(2) preparation of solid superacid
Firstly, ultrasonically dispersing zirconium-cerium composite oxide into deionized water, then adding ammonium molybdate into the deionized water, evaporating the ammonium molybdate to dryness in a water bath condition at the temperature of 90 ℃, roasting the evaporated material for 4-6 hours at the temperature of 500-800 ℃ to obtain MoO3MoO in an amount of 15 to 30 wt%3/ZrO2-CeO2Solid super acid;
(3) preparation of ionic liquid precursor TEAPS
Adding 1, 3-propane sultone and cyclohexane into an ultrasonic reactor, stirring and dissolving, then introducing argon for 30min, opening the ultrasonic reactor, keeping the power at 100-200W, then dropwise adding triethylamine into the reactor, reacting for 4-6 h to obtain a mixture, and then centrifuging, washing and drying the mixture to obtain a white powder solid, namely an ionic liquid precursor, which is marked as TEAPS; wherein the mass ratio of triethylamine to 1, 3-propane sultone is 1:1, the mass concentration of 1, 3-propane sultone in cyclohexane is 0.1 mol/L;
(4) in-situ loading of cerium-based solid ionic liquids
Adding MoO3/ZrO2-CeO2Adding solid superacid, phosphomolybdic acid, cerium nitrate and TEAPS into deionized water to obtain a mixture
Stirring the mixture at room temperature for 15min, transferring the mixture into an ultrasonic reactor, reacting for 4-6 h at 100-300W, and then sequentially centrifuging, washing and drying to obtain the composite catalyst of the solid superacid and the cerium-based solid ionic liquid; the cerium-based solid ionic liquid synthesized in the reaction process of phosphomolybdic acid, cerium nitrate and TEAPS is Ce0.33[TEAPS]2PMo12O40、Ce0.66[TEAPS]PMo12O40、Ce0.33[TEAPS]HPMo12O40One kind of (1).
3. The method of claim 2 for preparing a catalyst for use in the production of green diesel fuel additive, wherein: in the step (1), the mass concentration of the zirconyl nitrate solution is 0.2-0.4 mol/L, and the mass concentration of the cerium nitrate solution is 0.2-0.4 mol/L.
4. The method of claim 2 for preparing a catalyst for use in the production of green diesel fuel additive, wherein: in the step (4), the mass ratio of TEAPS to phosphomolybdic acid is (1-2): 1, the mass ratio of cerium nitrate to phosphomolybdic acid is (0.33-0.66): 1, and MoO in the composite catalyst3/ZrO2-CeO2The mass fraction of the solid superacid is 70-60 wt%.
CN202010633218.6A 2020-07-04 2020-07-04 Catalyst for producing green diesel oil additive and preparation method thereof Withdrawn CN111715281A (en)

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