CN111715280A - Catalyst for producing environment-friendly diesel additive and preparation method thereof - Google Patents

Catalyst for producing environment-friendly diesel additive and preparation method thereof Download PDF

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CN111715280A
CN111715280A CN202010633215.2A CN202010633215A CN111715280A CN 111715280 A CN111715280 A CN 111715280A CN 202010633215 A CN202010633215 A CN 202010633215A CN 111715280 A CN111715280 A CN 111715280A
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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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    • 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
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    • 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 an environment-friendly diesel additive and a preparation method thereof, which is prepared by preparing a zirconium-bismuth composite oxide, preparing a solid super acid, preparing an ionic liquid precursor MIMPS and preparing zirconium-based solid ionic liquid by in-situ loading, and is prepared by using WO3/ZrO2‑Bi2O3Catalyst for in-situ compounding solid superacid and zirconium-based solid ionic liquid, and WO in catalyst3/ZrO2‑Bi2O3The mass fraction of the solid super acid is 70-90 wt%. The invention can solve the problems of difficult separation of the catalyst and the product and poor stability caused by easy loss of reaction active components, and can also ensure that the catalyst is catalyzedThe catalyst keeps solid state, the acid amount and the acid strength of the catalyst are relatively moderate, the catalyst has no corrosion to a reactor, the catalytic efficiency is high, and the selectivity of the obtained main product is good.

Description

Catalyst for producing environment-friendly diesel additive and preparation method thereof
Technical Field
The invention belongs to the technical field of petrochemical industry, relates to a technology of a diesel additive, and particularly relates to a catalyst for producing an environment-friendly diesel additive and a preparation method of the catalyst.
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 liquid, and the cost is high, the separation is relatively complex, and the energy consumption of the subsequent 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 an environment-friendly diesel additive and a preparation method thereof, wherein the catalyst is prepared from WO3/ZrO2-Bi2O3The solid superacid is obtained by combining the solid superacid and the zirconium-based solid ionic liquid, not only can solve the problems of difficult separation of the catalyst and the product and poor stability caused by easy loss of reaction active components, but also can ensure that the catalyst keeps a solid state, the acid amount and the acid strength of the catalyst are relatively moderate, the catalyst has no corrosion to a reactor, the catalysis 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 an environmentally friendly diesel additive, and WO3/ZrO2-Bi2O3Catalyst for in-situ compounding of solid superacid and zirconium-based solid ionic liquid, in which catalyst WO3/ZrO2-Bi2O3The mass fraction of the solid superacid is 70-90 wt%, and the zirconium-based solid ionic liquid is Zr0.25[MIMPS]2PW12O40、Zr0.50[MIMPS]PW12O40、Zr0.25[MIMPS]HPW12O40One kind of (1).
On the other hand, the invention also discloses a preparation method of the catalyst for producing the environment-friendly diesel additive, which is realized by the following specific steps:
(1) preparation of zirconium bismuth composite oxide
Uniformly mixing a zirconyl nitrate solution and a bismuth nitrate solution, continuously stirring 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 550-750 ℃ for 5-7 h to obtain a zirconium-bismuth composite oxide; the mass ratio of zirconium and bismuth is 1: 3-3: 1, the addition amount of the urea is 10-20 times of the sum of the amounts of the zirconyl nitrate and the bismuth nitrate, and the addition amount of the PVA is 2-5 wt% of the total weight of the zirconyl nitrate and the bismuth nitrate;
(2) preparation of solid super acid:
ultrasonically dispersing a zirconium bismuth composite oxide into deionized water, adding ammonium paratungstate into the deionized water, evaporating the mixture to dryness in a water bath at 90 ℃, roasting the evaporated material at 600-800 ℃ for 3-5 hours to obtain WO3WO in an amount of 15 to 30 wt%3/ZrO2-Bi2O3Solid super acid;
(3) preparation of ionic liquid precursor MIMPS
Adding 1, 3-propane sultone and cyclohexane into a water bath, stirring and dissolving at 40 ℃, introducing argon for 30min, then dropwise adding N-methylimidazole into the mixture under the argon atmosphere, continuing to react for 4-6 h to obtain a milky mixture, and then centrifuging, washing and drying the mixture to obtain a white powder solid, namely an ionic liquid precursor, which is marked as MIMPS; wherein the mass ratio of the N-methylimidazole to the 1, 3-propane sultone is 1:1, and the mass concentration of the 1, 3-propane sultone in cyclohexane is 0.1 mol/L;
(4) in-situ loading of zirconium-based solid ionic liquids
Mixing WO3/ZrO2-Bi2O3Adding solid superacid, phosphotungstic acid, zirconyl nitrate and MIMPS into deionized water to obtain a mixture, stirring for 15min at room temperature, transferring the mixture into an ultrasonic reactor to react for 3-6 h at 100-200W, and then sequentially centrifuging, washing and drying to obtain the composite catalyst of the solid superacid and the zirconium-containing ionic liquid. Zirconium-based solid ions are prepared by the reaction of phosphotungstic acid, zirconyl nitrate and MIMPSLiquid Zr0.25[MIMPS]2PW12O40、Zr0.50[MIMPS]PW12O40、Zr0.25[MIMPS]HPW12O40One kind of (1).
In a preferred embodiment, in the step (1), the concentration of the zirconyl nitrate solution is 0.1-0.3 mol/L, and the concentration of the bismuth nitrate solution is 0.1-0.3 mol/L.
In a preferred embodiment, in the step (4), the ratio of the amounts of MIMPS and phosphotungstic acid is (1-2): 1, the ratio of the amounts of zirconyl nitrate and phosphotungstic acid is (0.25-0.50): 1, and the WO is contained in the composite catalyst3/ZrO2-Bi2O3The mass fraction of the solid superacid is 70-90 wt%.
Compared with the prior art, the invention has the following beneficial effects.
1) The zirconium-based solid ionic liquid exists in a solid form, on one hand, compared with the conventional liquid ionic liquid, the zirconium-based solid ionic liquid can be effectively separated from a product, and active components are not easy to lose, so that the zirconium-based solid ionic liquid is beneficial to cyclic utilization; on the other hand, the zirconium-based solid ionic 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 type ionic 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 increased, and higher catalytic activity and reaction stability are further embodied in the reaction process.
2) The zirconium-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 by-products on catalytic active points in the reaction process, but also can strengthen the zirconium-based solid ionic liquid and the solid super acid WO3/ZrO2-Bi2O3Synergistic effect between them. Meanwhile, the existence of various types of acid sites in the composite catalyst can prevent the similar catalytic activityThe deactivation of the sites results in a decrease in the reactivity of the catalyst.
3) Zirconium-based solid ionic liquids and WO3/ZrO2-Bi2O3The 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, zirconium-based solid ionic liquids have a relatively weak acid strength compared to conventional multi-sulfonate acidic ionic liquids, WO3/ZrO2-Bi2O3Compared 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 zirconium-based solid Ionic liquids4 2-With solid superacid WO3/ZrO2-Bi2O3ZrO of2-Bi2O3Can interact with each other to form a new reactive site SO4 2-/ZrO2-Bi2O3The 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
(1) Preparation of zirconium bismuth composite oxide
Uniformly mixing a zirconyl nitrate solution and a bismuth nitrate solution, continuously stirring for 25min, adding urea and PVA, continuously stirring for 35min, reacting for 24h at 80 ℃, centrifuging, washing and drying the obtained product, and roasting at 550 ℃ for 7 h to obtain a zirconium-bismuth composite oxide; the mass ratio of zirconium and bismuth is 1:2, the addition amount of the urea is 20 times of the sum of the mass amounts of the zirconium oxynitrate and the bismuth nitrate, and the addition amount of the PVA is 2 wt% of the total weight of the zirconium oxynitrate and the bismuth nitrate; the quantitative concentration of the zirconyl nitrate substance is 0.10mol/L, and the quantitative concentration of the bismuth nitrate substance is 0.3 mol/L;
(2) preparation of solid super acid:
firstly, ultrasonically dispersing a zirconium bismuth composite oxide into deionized water, then adding ammonium paratungstate into the zirconium bismuth composite oxide, evaporating the zirconium bismuth composite oxide to dryness in a 90 ℃ water bath condition, roasting the evaporated material at 600 ℃ for 5 hours to obtain WO3WO in an amount of 15 wt%3/ZrO2-Bi2O3Solid super acid;
(3) preparation of ionic liquid precursor MIMPS
Adding 1, 3-propane sultone and cyclohexane into a water bath, stirring and dissolving at 40 ℃, introducing argon for 30min, then dropwise adding N-methylimidazole into the mixture under the argon atmosphere, continuing to react for 4h to obtain a milky mixture, and then centrifuging, washing and drying the mixture to obtain a white powder solid, namely an ionic liquid precursor, which is marked as MIMPS; wherein the mass ratio of the N-methylimidazole to the 1, 3-propane sultone is 1:1, and the mass concentration of the 1, 3-propane sultone in cyclohexane is 0.1 mol/L;
(4) in-situ loading of zirconium-based solid ionic liquids
Mixing WO3/ZrO2-Bi2O3Adding solid superacid, phosphotungstic acid, zirconyl nitrate and MIMPS into deionized water to obtain a mixture, stirring at room temperature for 15min, transferring the mixture into an ultrasonic reactor to react for 6h at 100W, and then sequentially centrifuging, washing and drying to obtain the composite catalyst of the solid superacid and the zirconium-containing ionic liquid. Zr is prepared from phosphotungstic acid, zirconyl nitrate and MIMPS0.25[MIMPS]2PW12O40。
Wherein in the step (4), the mass ratio of MIMPS to phosphotungstic acid is 2:1, the mass ratio of zirconyl nitrate to phosphotungstic acid is 0.25:1, and WO is contained in the composite catalyst3/ZrO2-Bi2O3The mass fraction of the solid superacid is 70wt%, and the catalyst is labeledIs 1 #.
Adding 19.2 g of methanol, 54.0g of trioxymethylene and 3.66g of No. 1 catalyst into a 100mL high-pressure reaction kettle respectively, and filling N2Heating to 150 deg.c slowly under 2.0 MPa and stirring for 10 hr. The reaction product was cooled to room temperature, and the yield of PODE3-8 was 47.3% by gas chromatography and the conversion of methanol was 99.8%.
Example 2
(1) Preparation of zirconium bismuth composite oxide
Uniformly mixing a zirconyl nitrate solution and a bismuth nitrate solution, continuously stirring for 35min, adding urea and PVA, continuously stirring for 25min, reacting for 12h at 90 ℃, centrifuging, washing and drying the obtained product, and roasting at 750 ℃ for 5h to obtain a zirconium-bismuth composite oxide; the mass ratio of zirconium to bismuth is 3:1, the addition amount of the urea is 20 times of the sum of the mass amounts of the zirconium oxynitrate and the bismuth nitrate, and the addition amount of the PVA is 5 wt% of the total weight of the zirconium oxynitrate and the bismuth nitrate; the quantity concentration of the zirconyl nitrate substance is 0.3mol/L, and the quantity concentration of the bismuth nitrate substance is 0.15 mol/L;
(2) preparation of solid super acid:
firstly, ultrasonically dispersing a zirconium bismuth composite oxide into deionized water, then adding ammonium paratungstate into the zirconium bismuth composite oxide, evaporating the zirconium bismuth composite oxide to dryness in a 90 ℃ water bath condition, roasting the evaporated material at 800 ℃ for 3 hours to obtain WO3WO in an amount of 30 wt%3/ZrO2-Bi2O3Solid super acid;
(3) preparation of ionic liquid precursor MIMPS
Adding 1, 3-propane sultone and cyclohexane into a water bath, stirring and dissolving at 40 ℃, introducing argon for 30min, then dropwise adding N-methylimidazole into the mixture under the argon atmosphere, continuing to react for 6h to obtain a milky mixture, and then centrifuging, washing and drying the mixture to obtain a white powder solid, namely an ionic liquid precursor, which is marked as MIMPS; wherein the mass ratio of the N-methylimidazole to the 1, 3-propane sultone is 1:1, and the mass concentration of the 1, 3-propane sultone in cyclohexane is 0.1 mol/L;
(4) in-situ loading of zirconium-based solid ionic liquids
Mixing WO3/ZrO2-Bi2O3Adding solid superacid, phosphotungstic acid, zirconyl nitrate and MIMPS into deionized water to obtain a mixture, stirring at room temperature for 15min, transferring the mixture into an ultrasonic reactor to react for 3 h at 200W, and then sequentially centrifuging, washing and drying to obtain the composite catalyst of the solid superacid and the zirconium-containing ionic liquid. Zr is prepared from phosphotungstic acid, zirconyl nitrate and MIMPS0.50[MIMPS]PW12O40。
Wherein in the step (4), the mass ratio of MIMPS to phosphotungstic acid is 1:1, the mass ratio of zirconyl nitrate to phosphotungstic acid is 0.50:1, and WO is contained in the composite catalyst3/ZrO2-Bi2O3The mass fraction of the solid superacid is 90wt%, and the catalyst is marked as # 2.
Adding 19.2 g of methanol, 54.0g of trioxymethylene and 7.32g of No. 2 catalyst into a 100mL high-pressure reaction kettle respectively, and filling N2Heating to 150 deg.C slowly until the pressure is 2.0 MPa, and stirring for 5 hr. The reaction product was cooled to room temperature, and the yield of PODE3-8 by gas chromatography was 42.3%, and the conversion of methanol was 97.4%.
Example 3
(1) Preparation of zirconium bismuth composite oxide
Uniformly mixing a zirconium oxynitrate solution and a bismuth nitrate solution, continuously stirring for 30min, then adding urea and PVA into the mixture, continuously stirring for 30min, reacting for 18h at 85 ℃, centrifuging, washing and drying the obtained product, and roasting at 650 ℃ for 6h to obtain a zirconium-bismuth composite oxide; the quantity ratio of zirconium and bismuth is 1:1, the addition of the urea is 15 times of the sum of the quantities of the zirconyl nitrate and the bismuth nitrate, and the addition of the PVA is 3 wt% of the total weight of the zirconyl nitrate and the bismuth nitrate; the mass concentration of the zirconyl nitrate solution is 0.1mol/L, and the mass concentration of the bismuth nitrate solution is 0.1 mol/L;
(2) preparation of solid super acid:
firstly, ultrasonically dispersing zirconium bismuth composite oxide into deionized water, then adding ammonium paratungstate into the deionized water, and heating the mixture at 90 DEG CEvaporating to dryness in water bath, and roasting the evaporated material at 700 deg.C for 4 hr to obtain WO3WO in an amount of 25 wt%3/ZrO2-Bi2O3Solid super acid;
(3) preparation of ionic liquid precursor MIMPS
Adding 1, 3-propane sultone and cyclohexane into a water bath, stirring and dissolving at 40 ℃, introducing argon for 30min, then dropwise adding N-methylimidazole into the mixture under the argon atmosphere, continuing to react for 5h to obtain a milky mixture, and then centrifuging, washing and drying the mixture to obtain a white powder solid, namely an ionic liquid precursor, which is marked as MIMPS; wherein the mass ratio of the N-methylimidazole to the 1, 3-propane sultone is 1:1, and the mass concentration of the 1, 3-propane sultone in cyclohexane is 0.1 mol/L;
(4) in-situ loading of zirconium-based solid ionic liquids
Mixing WO3/ZrO2-Bi2O3Adding solid superacid, phosphotungstic acid, zirconyl nitrate and MIMPS into deionized water to obtain a mixture, stirring at room temperature for 15min, transferring the mixture into an ultrasonic reactor to react for 4.5 h at 150W, and then sequentially centrifuging, washing and drying to obtain the composite catalyst of the solid superacid and the zirconium-containing ionic liquid. Zr is prepared from phosphotungstic acid, zirconyl nitrate and MIMPS0.25[MIMPS]HPW12O40。
Wherein in the step (4), the mass ratio of MIMPS to phosphotungstic acid is 1:1, the mass ratio of zirconyl nitrate to phosphotungstic acid is 0.25:1, and WO is contained in the composite catalyst3/ZrO2-Bi2O3The mass fraction of the solid superacid is 80wt%, and the catalyst is marked as # 3.
Adding 19.2 g of methanol, 54.0g of trioxymethylene and 5.50g of No. 3 catalyst into a 100mL high-pressure reaction kettle respectively, and filling N2Heating to 150 deg.c slowly under 2.0 MPa and stirring for 8 hr. The reaction product was cooled to room temperature, and the yield of PODE3-8 was 45.8% by gas chromatography and the conversion of methanol was 99.9%.
Comparative example 1
(1) Preparation of zirconium bismuth composite oxide
Uniformly mixing a zirconium oxynitrate solution and a bismuth nitrate solution, continuously stirring for 30min, then adding urea and PVA into the mixture, continuously stirring for 30min, reacting for 18h at 85 ℃, centrifuging, washing and drying the obtained product, and roasting at 650 ℃ for 6h to obtain a zirconium-bismuth composite oxide; the quantity ratio of zirconium and bismuth is 1:1, the addition of the urea is 15 times of the sum of the quantities of the zirconyl nitrate and the bismuth nitrate, and the addition of the PVA is 3 wt% of the total weight of the zirconyl nitrate and the bismuth nitrate; the quantitative concentration of the zirconyl nitrate substance is 0.1mol/L, and the quantitative concentration of the bismuth nitrate substance is 0.1 mol/L;
(2) preparation of solid super acid:
firstly, ultrasonically dispersing a zirconium bismuth composite oxide into deionized water, then adding ammonium paratungstate into the zirconium bismuth composite oxide, evaporating the zirconium bismuth composite oxide to dryness in a 90 ℃ water bath condition, roasting the evaporated material at 700 ℃ for 4 hours to obtain WO3WO in an amount of 25 wt%3/ZrO2-Bi2O3Solid super acid;
the obtained solid super acid is marked as catalyst No. 4.
Adding 19.2 g of methanol, 54.0g of trioxymethylene and 5.50g of No. 4 catalyst into a 100mL high-pressure reaction kettle respectively, and filling N2Heating to 150 deg.c slowly under 2.0 MPa and stirring for 8 hr. The reaction product was cooled to room temperature, and the yield of PODE3-8 by gas chromatography was 34.6%, and the conversion of methanol was 79.3%.
Comparative example 2
(1) Preparation of ionic liquid precursor MIMPS
Adding 1, 3-propane sultone and cyclohexane into a water bath, stirring and dissolving at 40 ℃, introducing argon for 30min, then dropwise adding N-methylimidazole into the mixture under the argon atmosphere, continuing to react for 5h to obtain a milky mixture, and then centrifuging, washing and drying the mixture to obtain a white powder solid, namely an ionic liquid precursor, which is marked as MIMPS; wherein the mass ratio of the N-methylimidazole to the 1, 3-propane sultone is 1:1, and the mass concentration of the 1, 3-propane sultone in cyclohexane is 0.1 mol/L;
(2) preparation of zirconium-based solid ionic liquid
Adding phosphotungstic acid, zirconyl nitrate and MIMPS into deionized water to obtain a mixture, stirring for 15min at room temperature, transferring the mixture to an ultrasonic reactor to react for 4.5 h at 150W, and then sequentially centrifuging, washing and drying to obtain zirconium-based solid ionic liquid Zr0.25[MIMPS]HPW12O40。
Wherein, the mass ratio of MIMPS to phosphotungstic acid is 1:1, the mass ratio of zirconyl nitrate to phosphotungstic acid is 0.25:1, and the catalyst is marked as No. 5.
Adding 19.2 g of methanol, 54.0g of trioxymethylene and 5.50g of No. 5 catalyst into a 100mL high-pressure reaction kettle respectively, and filling N2Heating to 150 deg.c slowly under 2.0 MPa and stirring for 8 hr. The reaction product was cooled to room temperature, and the yield of PODE3-8 was 39.8% by gas chromatography and the conversion of methanol was 84.2%.
Example 4
The 1# catalyst was subjected to the following cycle test:
adding 19.2 g of methanol, 54.0g of trioxymethylene and 3.66g of No. 1 catalyst into a 100mL high-pressure reaction kettle respectively, and filling N2Heating to 150 deg.c slowly under 2.0 MPa and stirring for 10 hr. 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 169705DEST_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 an environment-friendly diesel additive is characterized in that: is as described in WO3/ZrO2-Bi2O3Catalyst for in-situ compounding of solid superacid and zirconium-based solid ionic liquid, in which catalyst WO3/ZrO2-Bi2O3The mass fraction of the solid superacid is 70-90 wt%, and the zirconium-based solid ionic liquid is Zr0.25[MIMPS]2PW12O40、Zr0.50[MIMPS]PW12O40、Zr0.25[MIMPS]HPW12O40One kind of (1).
2. A preparation method of a catalyst for producing an environment-friendly diesel additive is characterized by comprising the following specific steps:
(1) preparation of zirconium bismuth composite oxide
Uniformly mixing a zirconyl nitrate solution and a bismuth nitrate solution, continuously stirring 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 550-750 ℃ for 5-7 h to obtain a zirconium-bismuth composite oxide; the mass ratio of zirconium and bismuth is 1: 3-3: 1, the addition amount of the urea is 10-20 times of the sum of the amounts of the zirconyl nitrate and the bismuth nitrate, and the addition amount of the PVA is 2-5 wt% of the total weight of the zirconyl nitrate and the bismuth nitrate;
(2) preparation of solid super acid:
ultrasonically dispersing a zirconium bismuth composite oxide into deionized water, adding ammonium paratungstate into the deionized water, evaporating the mixture to dryness in a water bath at 90 ℃, roasting the evaporated material at 600-800 ℃ for 3-5 hours to obtain WO3WO in an amount of 15 to 30 wt%3/ZrO2-Bi2O3Solid super acid;
(3) preparation of ionic liquid precursor MIMPS
Adding 1, 3-propane sultone and cyclohexane into a water bath, stirring and dissolving at 40 ℃, introducing argon for 30min, then dropwise adding N-methylimidazole into the mixture under the argon atmosphere, continuing to react for 4-6 h to obtain a milky mixture, and then centrifuging, washing and drying the mixture to obtain a white powder solid, namely an ionic liquid precursor, which is marked as MIMPS; wherein the mass ratio of the N-methylimidazole to the 1, 3-propane sultone is 1:1, and the mass concentration of the 1, 3-propane sultone in cyclohexane is 0.1 mol/L;
(4) in-situ loading of zirconium-based solid ionic liquids
Mixing WO3/ZrO2-Bi2O3Adding solid superacid, phosphotungstic acid, zirconyl nitrate and MIMPS into deionized water to obtain a mixture, stirring for 15min at room temperature, transferring the mixture into an ultrasonic reactor to react for 3-6 h at 100-200W, and then sequentially centrifuging, washing and drying to obtain the composite catalyst of the solid superacid and the zirconium-containing ionic liquid, wherein the zirconium-based solid ionic liquid prepared from the phosphotungstic acid, the zirconyl nitrate and the MIMPS in the reaction process is Zr0.25[MIMPS]2PW12O40、Zr0.50[MIMPS]PW12O40Or Zr0.25[MIMPS]HPW12O40One kind of (1).
3. The method for preparing the catalyst for producing environmentally friendly diesel fuel additive as set forth in claim 2, wherein: in the step (1), the mass concentration of the zirconyl nitrate solution is 0.1-0.3 mol/L, and the mass concentration of the bismuth nitrate solution is 0.1-0.3 mol/L.
4. The method for preparing the catalyst for producing environmentally friendly diesel fuel additive as set forth in claim 2, wherein: in the step (4), the mass ratio of MIMPS to phosphotungstic acid is (1-2): 1, the mass ratio of zirconyl nitrate to phosphotungstic acid is (0.25-0.50): 1, and WO is contained in the composite catalyst3/ZrO2-Bi2O3The mass fraction of the solid superacid is 70-90 wt%.
CN202010633215.2A 2020-07-04 2020-07-04 Catalyst for producing environment-friendly diesel additive and preparation method thereof Withdrawn CN111715280A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113101970A (en) * 2021-04-22 2021-07-13 福建工程学院 Composite catalyst for producing methyl ethyl ketone and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113101970A (en) * 2021-04-22 2021-07-13 福建工程学院 Composite catalyst for producing methyl ethyl ketone and preparation method thereof

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