CN112915992B - Preparation method of biodiesel catalyst - Google Patents
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
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Abstract
The invention is applicable to the technical field of heat preservation materials, and provides a preparation method of a biodiesel catalyst, which comprises the following steps of preparing aluminum oxide, preparing ultrafine zinc oxide and then mixing to obtain the catalyst; according to the invention, the specific surface area of the catalyst is large and the catalyst has good mechanical strength by taking the alumina as a carrier and the ultrafine zinc oxide as a carrier, and the zinc oxide in the invention is the ultrafine zinc oxide, so that the high specific surface area of the catalyst is further increased, and the catalytic yield is improved; the ultrasonic treatment is carried out in the mixing process of the ultrafine zinc oxide and the aluminum oxide, so that the ultrafine zinc oxide and the aluminum oxide are well and uniformly combined, the utilization rate of the catalyst is further improved, and the yield is improved.
Description
Technical Field
The invention belongs to the technical field of heat preservation materials, and particularly relates to a preparation method of a biodiesel catalyst.
Background
Biodiesel refers to fatty acid methyl or ethyl esters formed by ester conversion of vegetable oils (such as rapeseed oil, soybean oil, peanut oil, corn oil, cottonseed oil, etc.), animal oils (such as fish oil, lard, tallow, sheep oil, etc.), waste oils or microbial oils and methanol or ethanol.
Biodiesel is a typical green energy source and has the characteristics of good environmental protection performance, good engine starting performance, good fuel performance, wide raw material sources, reproducibility and the like. The great development of biodiesel has important strategic significance for sustainable development of economy, replacement of propulsion energy, environmental pressure relief and urban air pollution control.
The biodiesel catalyst is all chemical auxiliary agents which accelerate chemical reaction, increase oil yield and improve fuel quality in the process of using animal and vegetable grease and leftovers for producing fuel oil. At present, biodiesel catalysts are mainly divided into two main types, namely, an acid/alkali homogeneous catalyst, a biological enzyme catalyst and a solid catalyst 3 main types which can be selected in the process of preparing biodiesel by using a chemical auxiliary agent for promoting esterification, such as an ester exchange method; 2. the catalyst is used for directly heating raw oil and performing thermal catalytic cracking, and has the main effects of decomposing large grease molecules with long carbon chains into diesel oil molecular structures with proper molecular weights, and the thermal cracking catalyst can crack the raw oil at a lower temperature, reduce energy consumption, improve the yield of biodiesel and endow the biodiesel with a low condensation point. The existing solid base catalyst has undeveloped structure, low specific surface area and low mechanical strength, and is unfavorable for the full utilization of the catalyst.
Disclosure of Invention
The invention aims to provide a preparation method of a biodiesel catalyst, which aims to solve the problems in the background technology.
In order to achieve the above purpose, the invention provides a preparation method of a biodiesel catalyst, which specifically comprises the following steps:
1) Preparation of alumina: mixing and stirring ferric nitrate, aluminum sulfate and water, continuously stirring at 90-100 ℃ to enable the solution to become a sticky substance, and then drying; calcining the dried substance, introducing hydrogen while calcining, cooling to mix the dried substance with hydrochloric acid, washing to neutrality, and drying to obtain aluminum oxide;
2) Preparing superfine zinc oxide: stirring a zinc sulfate solution with the concentration of 30% and a oxalic acid solution with the concentration of 15%, reacting for 10-15 min at normal temperature to obtain zinc oxalate precipitate, and then carrying out suction filtration and roasting to obtain ultrafine zinc oxide;
3) Then mixing and stirring the alumina prepared in the step 1) and the superfine zinc oxide prepared in the step 2), wherein the mass ratio of the alumina to the superfine zinc oxide is 5-8:1, simultaneously adding a coupling agent and 1.2 times of water, mixing and stirring, simultaneously carrying out ultrasonic treatment, then drying, roasting after drying to enable the roasting temperature to be 400-600 ℃, and roasting for 1-2 hours to obtain the catalyst.
Preferably, in step 1), the mass ratio of the ferric nitrate, the aluminum sulfate and the water is 1-3:25:200-300.
Preferably, in step 1), the mass ratio of ferric nitrate, aluminum sulfate and water is 2:25:250.
preferably, in step 1), the drying treatment is carried out at 120 to 140 ℃.
Preferably, in step 1), the specific steps of calcination are: calcining for 1-2h at 300-400 ℃ in sequence; calcining at 500-600 deg.c for 2-3 hr; calcining at 700-800 deg.C for 3-4 hr.
Preferably, in step 2), the mass ratio between the zinc sulfate solution and the oxalic acid solution is 1:2.
preferably, in step 2), the calcination is carried out at 300-400℃for a period of 2-3 hours.
Preferably, in step 3), the coupling agent is a titanate coupling agent.
Preferably, in step 3), the mass of the coupling agent is 1-2% of the total mass of alumina and ultramicro zinc oxide.
Preferably, in step 3), the ultrasonic treatment is such that an ultrasonic wave of 20KHz to 30KHz is used, and the ultrasonic treatment is performed for 15 to 20 minutes.
In summary, due to the adoption of the technical scheme, the method has the following beneficial effects:
the invention provides a preparation method of a biodiesel catalyst, wherein the specific surface area of the catalyst is large and the catalyst has good mechanical strength by taking aluminum oxide as a carrier and ultrafine zinc oxide as a carrier, and the zinc oxide in the catalyst is ultrafine zinc oxide to further increase the high specific surface area of the catalyst and improve the catalytic yield; the ultrasonic treatment is carried out in the mixing process of the ultrafine zinc oxide and the aluminum oxide, so that the ultrafine zinc oxide and the aluminum oxide are well and uniformly combined, the utilization rate of the catalyst is further improved, and the yield is improved.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The existing solid base catalyst has undeveloped structure, low specific surface area and low mechanical strength, and is not beneficial to the full utilization of the catalyst; in the invention, the specific surface area of the catalyst is large by taking alumina as a carrier and ultrafine zinc oxide as a carrier; the ultrasonic treatment is carried out in the mixing process of the ultrafine zinc oxide and the aluminum oxide, so that the ultrafine zinc oxide and the aluminum oxide are well and uniformly combined, the utilization rate of the catalyst is further improved, and the yield is improved.
Example 1
1) Preparation of alumina: mixing and stirring ferric nitrate, aluminum sulfate and water, wherein the mass ratio of the ferric nitrate to the aluminum sulfate to the water is 1:25:200, continuously stirring at 90 ℃ to enable the solution to become sticky, and then drying at 120 ℃; calcining the dried substance, introducing hydrogen while calcining, and calcining for 1h at 300 ℃ in sequence; calcining at 500 ℃ for 2 hours; calcining at 700 ℃ for 3 hours, cooling, mixing with hydrochloric acid, washing to neutrality, and drying to obtain alumina;
2) Preparing superfine zinc oxide: stirring a zinc sulfate solution with the concentration of 30% and a oxalic acid solution with the concentration of 15% at normal temperature, reacting for 10min to obtain zinc oxalate precipitate, performing suction filtration, and roasting at 300 ℃ for 2h to obtain ultrafine zinc oxide;
3) Mixing and stirring the aluminum oxide prepared in the step 1) and the superfine zinc oxide prepared in the step 2), wherein the mass ratio of the aluminum oxide to the superfine zinc oxide is 5:1 simultaneously adding titanate coupling agent and 1.2 times of water, wherein the mass of the coupling agent is 1% of the total mass of aluminum oxide and ultrafine zinc oxide, mixing and stirring, simultaneously introducing 25KHz ultrasonic waves into the coupling agent, carrying out ultrasonic treatment for 20min, drying, roasting after drying, so that the roasting temperature is 600 ℃, and roasting for 2h to obtain the catalyst.
Example 2
1) Preparation of alumina: mixing and stirring ferric nitrate, aluminum sulfate and water, wherein the mass ratio of the ferric nitrate to the aluminum sulfate to the water is 1:25:200, continuously stirring at 90 ℃ to enable the solution to become sticky, and then drying at 120 ℃; calcining the dried substance, introducing hydrogen while calcining, and calcining for 1h at 300 ℃ in sequence; calcining at 500 ℃ for 2 hours; calcining at 700 ℃ for 3 hours, cooling, mixing with hydrochloric acid, washing to neutrality, and drying to obtain alumina;
2) Preparing superfine zinc oxide: stirring a zinc sulfate solution with the concentration of 30% and a oxalic acid solution with the concentration of 15% at normal temperature, reacting for 10min to obtain zinc oxalate precipitate, performing suction filtration, and roasting at 300 ℃ for 2h to obtain ultrafine zinc oxide;
3) Mixing and stirring the aluminum oxide prepared in the step 1) and the superfine zinc oxide prepared in the step 2), wherein the mass ratio of the aluminum oxide to the superfine zinc oxide is 5.5:1 simultaneously adding titanate coupling agent and 1.2 times of water, wherein the mass of the coupling agent is 1% of the total mass of aluminum oxide and ultrafine zinc oxide, mixing and stirring, simultaneously introducing 25KHz ultrasonic waves into the coupling agent, carrying out ultrasonic treatment for 20min, drying, roasting after drying, so that the roasting temperature is 600 ℃, and roasting for 2h to obtain the catalyst.
Example 3
1) Preparation of alumina: mixing and stirring ferric nitrate, aluminum sulfate and water, wherein the mass ratio of the ferric nitrate to the aluminum sulfate to the water is 1:25:200, continuously stirring at 90 ℃ to enable the solution to become sticky, and then drying at 120 ℃; calcining the dried substance, introducing hydrogen while calcining, and calcining for 1h at 300 ℃ in sequence; calcining at 500 ℃ for 2 hours; calcining at 700 ℃ for 3 hours, cooling, mixing with hydrochloric acid, washing to neutrality, and drying to obtain alumina;
2) Preparing superfine zinc oxide: stirring a zinc sulfate solution with the concentration of 30% and a oxalic acid solution with the concentration of 15% at normal temperature, reacting for 10min to obtain zinc oxalate precipitate, performing suction filtration, and roasting at 300 ℃ for 2h to obtain ultrafine zinc oxide;
3) Mixing and stirring the aluminum oxide prepared in the step 1) and the superfine zinc oxide prepared in the step 2), wherein the mass ratio of the aluminum oxide to the superfine zinc oxide is 6:1 simultaneously adding titanate coupling agent and 1.2 times of water, wherein the mass of the coupling agent is 1% of the total mass of aluminum oxide and ultrafine zinc oxide, mixing and stirring, simultaneously introducing 25KHz ultrasonic waves into the coupling agent, carrying out ultrasonic treatment for 20min, drying, roasting after drying, so that the roasting temperature is 600 ℃, and roasting for 2h to obtain the catalyst.
Example 4
1) Preparation of alumina: mixing and stirring ferric nitrate, aluminum sulfate and water, wherein the mass ratio of the ferric nitrate to the aluminum sulfate to the water is 1:25:200, continuously stirring at 90 ℃ to enable the solution to become sticky, and then drying at 120 ℃; calcining the dried substance, introducing hydrogen while calcining, and calcining for 1h at 300 ℃ in sequence; calcining at 500 ℃ for 2 hours; calcining at 700 ℃ for 3 hours, cooling, mixing with hydrochloric acid, washing to neutrality, and drying to obtain alumina;
2) Preparing superfine zinc oxide: stirring a zinc sulfate solution with the concentration of 30% and a oxalic acid solution with the concentration of 15% at normal temperature, reacting for 10min to obtain zinc oxalate precipitate, performing suction filtration, and roasting at 300 ℃ for 2h to obtain ultrafine zinc oxide;
3) Mixing and stirring the aluminum oxide prepared in the step 1) and the superfine zinc oxide prepared in the step 2), wherein the mass ratio of the aluminum oxide to the superfine zinc oxide is 6.5:1 simultaneously adding titanate coupling agent and 1.2 times of water, wherein the mass of the coupling agent is 1% of the total mass of aluminum oxide and ultrafine zinc oxide, mixing and stirring, simultaneously introducing 25KHz ultrasonic waves into the coupling agent, carrying out ultrasonic treatment for 20min, drying, roasting after drying, so that the roasting temperature is 600 ℃, and roasting for 2h to obtain the catalyst.
Example 5
1) Preparation of alumina: mixing and stirring ferric nitrate, aluminum sulfate and water, wherein the mass ratio of the ferric nitrate to the aluminum sulfate to the water is 1:25:200, continuously stirring at 90 ℃ to enable the solution to become sticky, and then drying at 120 ℃; calcining the dried substance, introducing hydrogen while calcining, and calcining for 1h at 300 ℃ in sequence; calcining at 500 ℃ for 2 hours; calcining at 700 ℃ for 3 hours, cooling, mixing with hydrochloric acid, washing to neutrality, and drying to obtain alumina;
2) Preparing superfine zinc oxide: stirring a zinc sulfate solution with the concentration of 30% and a oxalic acid solution with the concentration of 15% at normal temperature, reacting for 10min to obtain zinc oxalate precipitate, performing suction filtration, and roasting at 300 ℃ for 2h to obtain ultrafine zinc oxide;
3) Mixing and stirring the aluminum oxide prepared in the step 1) and the superfine zinc oxide prepared in the step 2), wherein the mass ratio of the aluminum oxide to the superfine zinc oxide is 7:1 simultaneously adding titanate coupling agent and 1.2 times of water, wherein the mass of the coupling agent is 1% of the total mass of aluminum oxide and ultrafine zinc oxide, mixing and stirring, simultaneously introducing 25KHz ultrasonic waves into the coupling agent, carrying out ultrasonic treatment for 20min, drying, roasting after drying, so that the roasting temperature is 600 ℃, and roasting for 2h to obtain the catalyst.
Example 6
1) Preparation of alumina: mixing and stirring ferric nitrate, aluminum sulfate and water, wherein the mass ratio of the ferric nitrate to the aluminum sulfate to the water is 1:25:200, continuously stirring at 90 ℃ to enable the solution to become sticky, and then drying at 120 ℃; calcining the dried substance, introducing hydrogen while calcining, and calcining for 1h at 300 ℃ in sequence; calcining at 500 ℃ for 2 hours; calcining at 700 ℃ for 3 hours, cooling, mixing with hydrochloric acid, washing to neutrality, and drying to obtain alumina;
2) Preparing superfine zinc oxide: stirring a zinc sulfate solution with the concentration of 30% and a oxalic acid solution with the concentration of 15% at normal temperature, reacting for 10min to obtain zinc oxalate precipitate, performing suction filtration, and roasting at 300 ℃ for 2h to obtain ultrafine zinc oxide;
3) Mixing and stirring the aluminum oxide prepared in the step 1) and the superfine zinc oxide prepared in the step 2), wherein the mass ratio of the aluminum oxide to the superfine zinc oxide is 7.5:1 simultaneously adding titanate coupling agent and 1.2 times of water, wherein the mass of the coupling agent is 1% of the total mass of aluminum oxide and ultrafine zinc oxide, mixing and stirring, simultaneously introducing 25KHz ultrasonic waves into the coupling agent, carrying out ultrasonic treatment for 20min, drying, roasting after drying, so that the roasting temperature is 600 ℃, and roasting for 2h to obtain the catalyst.
Example 7
1) Preparation of alumina: mixing and stirring ferric nitrate, aluminum sulfate and water, wherein the mass ratio of the ferric nitrate to the aluminum sulfate to the water is 1:25:200, continuously stirring at 90 ℃ to enable the solution to become sticky, and then drying at 120 ℃; calcining the dried substance, introducing hydrogen while calcining, and calcining for 1h at 300 ℃ in sequence; calcining at 500 ℃ for 2 hours; calcining at 700 ℃ for 3 hours, cooling, mixing with hydrochloric acid, washing to neutrality, and drying to obtain alumina;
2) Preparing superfine zinc oxide: stirring a zinc sulfate solution with the concentration of 30% and a oxalic acid solution with the concentration of 15% at normal temperature, reacting for 10min to obtain zinc oxalate precipitate, performing suction filtration, and roasting at 300 ℃ for 2h to obtain ultrafine zinc oxide;
3) Mixing and stirring the aluminum oxide prepared in the step 1) and the superfine zinc oxide prepared in the step 2), wherein the mass ratio of the aluminum oxide to the superfine zinc oxide is 8:1 simultaneously adding titanate coupling agent and 1.2 times of water, wherein the mass of the coupling agent is 1% of the total mass of aluminum oxide and ultrafine zinc oxide, mixing and stirring, simultaneously introducing 25KHz ultrasonic waves into the coupling agent, carrying out ultrasonic treatment for 20min, drying, roasting after drying, so that the roasting temperature is 600 ℃, and roasting for 2h to obtain the catalyst.
Example 8
1) Preparation of alumina: mixing and stirring ferric nitrate, aluminum sulfate and water, wherein the mass ratio of the ferric nitrate to the aluminum sulfate to the water is 1:25:200, continuously stirring at 90 ℃ to enable the solution to become sticky, and then drying at 120 ℃; calcining the dried substance, introducing hydrogen while calcining, and calcining for 1h at 300 ℃ in sequence; calcining at 500 ℃ for 2 hours; calcining at 700 ℃ for 3 hours, cooling, mixing with hydrochloric acid, washing to neutrality, and drying to obtain alumina;
2) Preparing superfine zinc oxide: stirring a zinc sulfate solution with the concentration of 30% and a oxalic acid solution with the concentration of 15% at normal temperature, reacting for 10min to obtain zinc oxalate precipitate, performing suction filtration, and roasting at 400 ℃ for 1h to obtain ultrafine zinc oxide;
3) Mixing and stirring the aluminum oxide prepared in the step 1) and the superfine zinc oxide prepared in the step 2), wherein the mass ratio of the aluminum oxide to the superfine zinc oxide is 7:1 simultaneously adding titanate coupling agent and 1.2 times of water, wherein the mass of the coupling agent is 1% of the total mass of aluminum oxide and ultrafine zinc oxide, mixing and stirring, simultaneously introducing 25KHz ultrasonic waves into the coupling agent, carrying out ultrasonic treatment for 20min, drying, roasting after drying, so that the roasting temperature is 600 ℃, and roasting for 2h to obtain the catalyst.
Example 9
1) Preparation of alumina: mixing and stirring ferric nitrate, aluminum sulfate and water, wherein the mass ratio of the ferric nitrate to the aluminum sulfate to the water is 1:25:200, continuously stirring at 90 ℃ to enable the solution to become sticky, and then drying at 120 ℃; calcining the dried substance, introducing hydrogen while calcining, and calcining for 1h at 300 ℃ in sequence; calcining at 500 ℃ for 2 hours; calcining at 700 ℃ for 3 hours, cooling, mixing with hydrochloric acid, washing to neutrality, and drying to obtain alumina;
2) Preparing superfine zinc oxide: stirring a zinc sulfate solution with the concentration of 30% and a oxalic acid solution with the concentration of 15% at normal temperature, reacting for 10min to obtain zinc oxalate precipitate, performing suction filtration, and roasting at 300 ℃ for 2h to obtain ultrafine zinc oxide;
3) Mixing and stirring the aluminum oxide prepared in the step 1) and the superfine zinc oxide prepared in the step 2), wherein the mass ratio of the aluminum oxide to the superfine zinc oxide is 7:1 simultaneously adding titanate coupling agent and 1.2 times of water, wherein the mass of the coupling agent is 2% of the total mass of aluminum oxide and ultrafine zinc oxide, mixing and stirring, simultaneously introducing 25KHz ultrasonic waves into the coupling agent, carrying out ultrasonic treatment for 20min, drying, roasting after drying, so that the roasting temperature is 600 ℃, and roasting for 2h to obtain the catalyst.
Example 10
1) Preparation of alumina: mixing and stirring ferric nitrate, aluminum sulfate and water, wherein the mass ratio of the ferric nitrate to the aluminum sulfate to the water is 1:25:200, continuously stirring at 90 ℃ to enable the solution to become sticky, and then drying at 120 ℃; calcining the dried substance, introducing hydrogen while calcining, and calcining for 1h at 300 ℃ in sequence; calcining at 500 ℃ for 2 hours; calcining at 700 ℃ for 3 hours, cooling, mixing with hydrochloric acid, washing to neutrality, and drying to obtain alumina;
2) Preparing superfine zinc oxide: stirring a zinc sulfate solution with the concentration of 30% and a oxalic acid solution with the concentration of 15% at normal temperature, reacting for 10min to obtain zinc oxalate precipitate, performing suction filtration, and roasting at 300 ℃ for 2h to obtain ultrafine zinc oxide;
3) Mixing and stirring the aluminum oxide prepared in the step 1) and the superfine zinc oxide prepared in the step 2), wherein the mass ratio of the aluminum oxide to the superfine zinc oxide is 7:1 simultaneously adding titanate coupling agent and 1.2 times of water, wherein the mass of the coupling agent is 1% of the total mass of aluminum oxide and ultrafine zinc oxide, mixing and stirring, simultaneously introducing 20KHz ultrasonic waves into the coupling agent, carrying out ultrasonic treatment for 20min, drying, roasting after drying, so that the roasting temperature is 600 ℃, and roasting for 2h to obtain the catalyst.
Example 11
1) Preparation of alumina: mixing and stirring ferric nitrate, aluminum sulfate and water, wherein the mass ratio of the ferric nitrate to the aluminum sulfate to the water is 1:25:200, continuously stirring at 90 ℃ to enable the solution to become sticky, and then drying at 120 ℃; calcining the dried substance, introducing hydrogen while calcining, and calcining for 1h at 300 ℃ in sequence; calcining at 500 ℃ for 2 hours; calcining at 700 ℃ for 3 hours, cooling, mixing with hydrochloric acid, washing to neutrality, and drying to obtain alumina;
2) Preparing superfine zinc oxide: stirring a zinc sulfate solution with the concentration of 30% and a oxalic acid solution with the concentration of 15% at normal temperature, reacting for 10min to obtain zinc oxalate precipitate, performing suction filtration, and roasting at 300 ℃ for 2h to obtain ultrafine zinc oxide;
3) Mixing and stirring the aluminum oxide prepared in the step 1) and the superfine zinc oxide prepared in the step 2), wherein the mass ratio of the aluminum oxide to the superfine zinc oxide is 7:1 simultaneously adding titanate coupling agent and 1.2 times of water, wherein the mass of the coupling agent is 1% of the total mass of aluminum oxide and ultrafine zinc oxide, mixing and stirring, simultaneously introducing 30KHz ultrasonic waves into the coupling agent, carrying out ultrasonic treatment for 15min, drying, roasting after drying, so that the roasting temperature is 600 ℃, and roasting for 2h to obtain the catalyst.
Example 12
1) Preparation of alumina: mixing and stirring ferric nitrate, aluminum sulfate and water, wherein the mass ratio of the ferric nitrate to the aluminum sulfate to the water is 1:25:200, continuously stirring at 90 ℃ to enable the solution to become sticky, and then drying at 120 ℃; calcining the dried substance, introducing hydrogen while calcining, and calcining for 1h at 300 ℃ in sequence; calcining at 500 ℃ for 2 hours; calcining at 700 ℃ for 3 hours, cooling, mixing with hydrochloric acid, washing to neutrality, and drying to obtain alumina;
2) Preparing superfine zinc oxide: stirring a zinc sulfate solution with the concentration of 30% and a oxalic acid solution with the concentration of 15% at normal temperature, reacting for 10min to obtain zinc oxalate precipitate, performing suction filtration, and roasting at 300 ℃ for 2h to obtain ultrafine zinc oxide;
3) Mixing and stirring the aluminum oxide prepared in the step 1) and the superfine zinc oxide prepared in the step 2), wherein the mass ratio of the aluminum oxide to the superfine zinc oxide is 7:1 simultaneously adding titanate coupling agent and 1.2 times of water, wherein the mass of the coupling agent is 1% of the total mass of aluminum oxide and ultrafine zinc oxide, mixing and stirring, simultaneously introducing 25KHz ultrasonic waves into the coupling agent, carrying out ultrasonic treatment for 20min, drying, roasting after drying, so that the roasting temperature is 400 ℃, and roasting for 2h to obtain the catalyst.
Example 13
1) Preparation of alumina: mixing and stirring ferric nitrate, aluminum sulfate and water, wherein the mass ratio of the ferric nitrate to the aluminum sulfate to the water is 1:25:200, continuously stirring at 90 ℃ to enable the solution to become sticky, and then drying at 120 ℃; calcining the dried substance, introducing hydrogen while calcining, and calcining for 1h at 300 ℃ in sequence; calcining at 500 ℃ for 2 hours; calcining at 700 ℃ for 3 hours, cooling, mixing with hydrochloric acid, washing to neutrality, and drying to obtain alumina;
2) Preparing superfine zinc oxide: stirring a zinc sulfate solution with the concentration of 30% and a oxalic acid solution with the concentration of 15% at normal temperature, reacting for 10min to obtain zinc oxalate precipitate, performing suction filtration, and roasting at 300 ℃ for 2h to obtain ultrafine zinc oxide;
3) Mixing and stirring the aluminum oxide prepared in the step 1) and the superfine zinc oxide prepared in the step 2), wherein the mass ratio of the aluminum oxide to the superfine zinc oxide is 7:1 simultaneously adding titanate coupling agent and 1.2 times of water, wherein the mass of the coupling agent is 1% of the total mass of aluminum oxide and ultrafine zinc oxide, mixing and stirring, simultaneously introducing 25KHz ultrasonic waves into the coupling agent, carrying out ultrasonic treatment for 20min, drying, roasting after drying, so that the roasting temperature is 500 ℃, and roasting for 2h to obtain the catalyst.
Example 14
1) Preparation of alumina: mixing and stirring ferric nitrate, aluminum sulfate and water, wherein the mass ratio of the ferric nitrate to the aluminum sulfate to the water is 1:25:200, continuously stirring at 90 ℃ to enable the solution to become sticky, and then drying at 120 ℃; calcining the dried substance, introducing hydrogen while calcining, and calcining for 1h at 400 ℃ in sequence; calcining at 600 ℃ for 2 hours; calcining at 800 ℃ for 3 hours, cooling, mixing with hydrochloric acid, washing to neutrality, and drying to obtain alumina;
2) Preparing superfine zinc oxide: stirring a zinc sulfate solution with the concentration of 30% and a oxalic acid solution with the concentration of 15% at normal temperature, reacting for 10min to obtain zinc oxalate precipitate, performing suction filtration, and roasting at 300 ℃ for 2h to obtain ultrafine zinc oxide;
3) Mixing and stirring the aluminum oxide prepared in the step 1) and the superfine zinc oxide prepared in the step 2), wherein the mass ratio of the aluminum oxide to the superfine zinc oxide is 7:1 simultaneously adding titanate coupling agent and 1.2 times of water, wherein the mass of the coupling agent is 1% of the total mass of aluminum oxide and ultrafine zinc oxide, mixing and stirring, simultaneously introducing 25KHz ultrasonic waves into the coupling agent, carrying out ultrasonic treatment for 20min, drying, roasting after drying, so that the roasting temperature is 600 ℃, and roasting for 2h to obtain the catalyst.
Example 15
1) Preparation of alumina: mixing and stirring ferric nitrate, aluminum sulfate and water, wherein the mass ratio of the ferric nitrate to the aluminum sulfate to the water is 1:25:200, continuously stirring at 90 ℃ to enable the solution to become sticky, and then drying at 120 ℃; calcining the dried substance, introducing hydrogen while calcining, and calcining for 2 hours at 300 ℃ in sequence; calcining at 500 ℃ for 3 hours; calcining at 700 ℃ for 4 hours, cooling, mixing and washing with hydrochloric acid, washing to be neutral, and drying to obtain alumina;
2) Preparing superfine zinc oxide: stirring a zinc sulfate solution with the concentration of 30% and a oxalic acid solution with the concentration of 15% at normal temperature, reacting for 10min to obtain zinc oxalate precipitate, performing suction filtration, and roasting at 300 ℃ for 2h to obtain ultrafine zinc oxide;
3) Mixing and stirring the aluminum oxide prepared in the step 1) and the superfine zinc oxide prepared in the step 2), wherein the mass ratio of the aluminum oxide to the superfine zinc oxide is 7:1 simultaneously adding titanate coupling agent and 1.2 times of water, wherein the mass of the coupling agent is 1% of the total mass of aluminum oxide and ultrafine zinc oxide, mixing and stirring, simultaneously introducing 25KHz ultrasonic waves into the coupling agent, carrying out ultrasonic treatment for 20min, drying, roasting after drying, so that the roasting temperature is 600 ℃, and roasting for 2h to obtain the catalyst.
Comparative example 1
1) Preparation of alumina: mixing and stirring ferric nitrate, aluminum sulfate and water, wherein the mass ratio of the ferric nitrate to the aluminum sulfate to the water is 1:25:200, continuously stirring at 90 ℃ to enable the solution to become sticky, and then drying at 120 ℃; calcining the dried substance, introducing hydrogen while calcining, and calcining for 1h at 300 ℃ in sequence; calcining at 500 ℃ for 2 hours; calcining at 700 ℃ for 3 hours, cooling, mixing with hydrochloric acid, washing to neutrality, and drying to obtain alumina;
2) Mixing and stirring the aluminum oxide and the zinc oxide prepared in the step 1), wherein the mass ratio of the aluminum oxide to the zinc oxide is 7:1 simultaneously adding titanate coupling agent and 1.2 times of water, wherein the mass of the coupling agent is 1% of the total mass of aluminum oxide and zinc oxide, mixing and stirring, simultaneously introducing 25KHz ultrasonic waves into the coupling agent, carrying out ultrasonic treatment for 20min, drying, and roasting after drying to obtain the catalyst, wherein the roasting temperature is 600 ℃, and roasting is carried out for 2 h.
Comparative example 2
1) Preparation of alumina: mixing and stirring ferric nitrate, aluminum sulfate and water, wherein the mass ratio of the ferric nitrate to the aluminum sulfate to the water is 1:25:200, continuously stirring at 90 ℃ to enable the solution to become sticky, and then drying at 120 ℃; calcining the dried substance, introducing hydrogen while calcining, and calcining for 1h at 300 ℃ in sequence; calcining at 500 ℃ for 2 hours; calcining at 700 ℃ for 3 hours, cooling, mixing with hydrochloric acid, washing to neutrality, and drying to obtain alumina;
2) Preparing superfine zinc oxide: stirring a zinc sulfate solution with the concentration of 30% and a oxalic acid solution with the concentration of 15% at normal temperature, reacting for 10min to obtain zinc oxalate precipitate, performing suction filtration, and roasting at 300 ℃ for 2h to obtain ultrafine zinc oxide;
3) Mixing and stirring the aluminum oxide prepared in the step 1) and the superfine zinc oxide prepared in the step 2), wherein the mass ratio of the aluminum oxide to the superfine zinc oxide is 7:1 simultaneously adding titanate coupling agent and 1.2 times of water, wherein the mass of the coupling agent is 1% of the total mass of the aluminum oxide and the superfine zinc oxide, mixing and stirring, then drying, and roasting after drying to obtain the catalyst, wherein the roasting temperature is 600 ℃ and roasting is 2 hours.
Comparative example 3
1) Preparation of alumina: mixing and stirring ferric nitrate, aluminum sulfate and water, wherein the mass ratio of the ferric nitrate to the aluminum sulfate to the water is 1:25:200, continuously stirring at 90 ℃ to enable the solution to become sticky, and then drying at 120 ℃; calcining the dried substance, introducing hydrogen while calcining, and calcining for 1h at 300 ℃ in sequence; calcining at 500 ℃ for 2 hours; calcining at 700 ℃ for 3 hours, cooling, mixing with hydrochloric acid, washing to neutrality, and drying to obtain alumina;
2) Mixing and stirring the aluminum oxide and the zinc oxide prepared in the step 1), wherein the mass ratio of the aluminum oxide to the zinc oxide is 7:1 simultaneously adding titanate coupling agent and 1.2 times of water, wherein the mass of the coupling agent is 1% of the total mass of aluminum oxide and zinc oxide, mixing and stirring, then drying, roasting after drying to obtain the catalyst, wherein the roasting temperature is 600 ℃, and roasting is carried out for 2 hours.
The catalysts prepared in examples 1 to 15 and comparative examples 1 to 3 were used to catalyze the production of biodiesel, respectively, and the average yield of biodiesel was calculated to be 100g of soybean oil, 3g of solid base catalyst and 40g of methanol, and reacted.
TABLE 1
TABLE 2
To sum up: the invention provides a preparation method of a biodiesel catalyst, wherein the specific surface area of the catalyst is large and the catalyst has good mechanical strength by taking aluminum oxide as a carrier and ultrafine zinc oxide as a carrier, and the zinc oxide in the catalyst is ultrafine zinc oxide to further increase the high specific surface area of the catalyst and improve the catalytic yield; the ultrasonic treatment is carried out in the mixing process of the ultrafine zinc oxide and the aluminum oxide, so that the ultrafine zinc oxide and the aluminum oxide are well and uniformly combined, the utilization rate of the catalyst is further improved, and the yield is improved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (7)
1. The preparation method of the biodiesel catalyst is characterized by comprising the following steps of:
1) Preparation of alumina: mixing and stirring ferric nitrate, aluminum sulfate and water, continuously stirring at 90-100 ℃ to enable the solution to become a sticky substance, and then drying; calcining the dried substance, introducing hydrogen while calcining, cooling to mix the dried substance with hydrochloric acid, washing to neutrality, and drying to obtain aluminum oxide;
2) Preparing superfine zinc oxide: stirring a zinc sulfate solution with the concentration of 30% and a oxalic acid solution with the concentration of 15%, reacting for 10-15 min at normal temperature to obtain zinc oxalate precipitate, and then carrying out suction filtration and roasting to obtain ultrafine zinc oxide;
3) Then mixing and stirring the alumina prepared in the step 1) and the superfine zinc oxide prepared in the step 2), wherein the mass ratio of the alumina to the superfine zinc oxide is 5-8:1, simultaneously adding a coupling agent and 1.2 times of water, mixing and stirring, simultaneously performing ultrasonic treatment, then drying, roasting after drying to enable the roasting temperature to be 400-600 ℃, and roasting for 1-2 hours to obtain a catalyst;
in the step 3), the coupling agent is a titanate coupling agent; in the step 3), the mass of the coupling agent is 1-2% of the total mass of the aluminum oxide and the superfine zinc oxide; in step 3), the ultrasonic treatment is carried out by adopting ultrasonic waves of 20KHz-30KHz for 15-20min.
2. The method for preparing a biodiesel catalyst according to claim 1, wherein in step 1), the mass ratio of ferric nitrate, aluminum sulfate and water is 1-3:25:200-300.
3. The method for preparing a biodiesel catalyst according to claim 2, wherein in step 1), the mass ratio of ferric nitrate, aluminum sulfate and water is 2:25:250.
4. the method for preparing a biodiesel catalyst according to claim 1, wherein in step 1), the drying treatment is performed at 120 to 140 ℃.
5. The method for preparing a biodiesel catalyst according to claim 1, wherein in step 1), the specific steps of calcination are: calcining for 1-2h at 300-400 ℃ in sequence; calcining at 500-600 deg.c for 2-3 hr; calcining at 700-800 deg.C for 3-4 hr.
6. The method for preparing a biodiesel catalyst according to claim 1, wherein in the step 2), the mass ratio between the zinc sulfate solution and the oxalic acid solution is 1:2.
7. the method for preparing a biodiesel catalyst according to claim 1, wherein in step 2), the calcination is performed at 300 to 400 ℃ for 2 to 3 hours.
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| US5908946A (en) * | 1996-08-08 | 1999-06-01 | Institut Francais Du Petrole | Process for the production of esters from vegetable oils or animal oils alcohols |
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