阅读说明：本技术 一种动植物油加氢直接脱氧催化剂的制备方法 (Preparation method of animal and vegetable oil hydrogenation direct deoxidation catalyst ) 是由 马斐 罗均龙 刘洪� 齐恺男 于 2020-04-01 设计创作，主要内容包括：本发明公开了一种动植物油加氢直接脱氧催化剂的制备方法,包括以下步骤：S1,将SB粉与水搅拌均匀,再加入胶溶剂搅拌均匀,形成粘合剂；S2,将拟薄水铝石与田菁粉在碾压机内混合均匀后,加水,再加入S1中制备的粘合剂搅拌均匀后,制得成型前料,所述拟薄水铝石中含有二氧化硅,所述田菁粉中含有氧化铝；S3,将S2中成型前料在挤条机上挤条成型,经养生、干燥、焙烧制得催化剂载体；不仅提高了成型载体的外比表面积,同时可提高活性金属在载体表面的负载量和分散程度,并提高了助剂硅和磷与活性金属的协同作用,降低了循环氢提纯的难度及生产和投资成本,本发明催化剂尤其适用于动植物油酯大分子的加氢直接脱氧反应。(The invention discloses a preparation method of a direct deoxidation catalyst for animal and vegetable oil hydrogenation, which comprises the following steps: s1, stirring the SB powder and water uniformly, adding a peptizing agent, and stirring uniformly to form an adhesive; s2, mixing the pseudo-boehmite and sesbania powder uniformly in a rolling machine, adding water, adding the adhesive prepared in S1, and stirring uniformly to prepare a material before forming, wherein the pseudo-boehmite contains silicon dioxide, and the sesbania powder contains aluminum oxide; s3, extruding the forming material in the S2 on a strip extruding machine for forming, curing, drying and roasting to obtain a catalyst carrier; the catalyst provided by the invention not only improves the external specific surface area of the formed carrier, but also can improve the loading capacity and dispersion degree of active metal on the surface of the carrier, improves the synergistic effect of the auxiliary agents of silicon and phosphorus and the active metal, and reduces the difficulty in purification of circulating hydrogen and the production and investment costs.)

1. A preparation method of a direct deoxidation catalyst for animal and vegetable oil hydrogenation is characterized by comprising the following steps:

s1, stirring the SB powder and water uniformly, adding a peptizing agent, and stirring uniformly to form an adhesive;

s2, mixing the pseudo-boehmite and sesbania powder uniformly in a rolling machine, adding water, adding the adhesive prepared in S1, and stirring uniformly to prepare a material before forming, wherein the pseudo-boehmite contains silicon dioxide, and the sesbania powder contains aluminum oxide;

s3, extruding the forming material in the S2 on a strip extruding machine for forming, curing, drying and roasting to obtain a catalyst carrier;

s4, pre-impregnating the catalyst carrier in the S3 with an auxiliary agent solution at a certain temperature, and carrying out health preserving, drying and secondary roasting to obtain an auxiliary agent-containing carrier;

and S5, impregnating the assistant-containing carrier in the S4 with a metal salt solution, and carrying out health preserving, drying and three-stage roasting to obtain the catalyst.

2. The preparation method of the animal and vegetable oil hydrogenation direct deoxidation catalyst according to the claim 1 is characterized in that: the mass ratio of the SB powder to the water is 0.15:1-0.6: 1.

3. The preparation method of the animal and vegetable oil hydrogenation direct deoxidation catalyst according to the claim 1 is characterized in that: the peptizing agent is a mixture of organic acid or inorganic acid and water, the mass ratio of the organic acid or the inorganic acid to the water in the peptizing agent is 0.015:1-0.65:1, and the mass ratio of the peptizing agent to the SB powder is 0.05:1-0.1: 1.

4. The preparation method of the animal and vegetable oil hydrogenation direct deoxidation catalyst according to the claim 1 is characterized in that: the content of silicon dioxide in the pseudo-boehmite is 1% -30%, and the adding amount of aluminum oxide in the sesbania powder is 3%; the mass ratio of the adhesive to the alumina in the pseudo-boehmite is 1.5:1-3: 1.

5. The preparation method of the animal and vegetable oil hydrogenation direct deoxidation catalyst according to the claim 1 is characterized in that: when the pseudo-boehmite is mixed with the sesbania powder, water is added, and the water addition amount is 10-80% of the content of alumina in the pseudo-boehmite.

6. The preparation method of the animal and vegetable oil hydrogenation direct deoxidation catalyst according to the claim 1 is characterized in that: in the S3, in the curing process, the curing temperature of the additive-containing carrier is 25-28 ℃ at room temperature for 4-48 h; the drying temperature is 70-150 ℃, and the drying time is 2-6 h; the heating rate of the roasting condition is 50-200 ℃/h, the roasting temperature is 400-600-.

7. The preparation method of the animal and vegetable oil hydrogenation direct deoxidation catalyst according to the claim 1 is characterized in that: in the S4, the auxiliary agent is phosphide such as phosphoric acid, phosphorous acid, ammonium phosphate, diammonium hydrogen phosphate or ammonium dihydrogen phosphate, the impregnation amount of phosphorus is 0.2-8% of the catalyst carrier, a saturated impregnation mode is adopted, the solution temperature of the auxiliary agent is 25-70 ℃, the curing temperature of the auxiliary agent-containing carrier is 25-28 ℃, and the curing time is 4-48 hours; the drying temperature is 70-150 ℃, and the drying time is 2-6 h; the second-stage roasting comprises two times of roasting, wherein in the first-stage roasting, the roasting is carried out from room temperature 25 ℃ to 200-230 ℃, the heating rate is 30-200 ℃/h, and the constant-temperature roasting is carried out for 0.5-2 h; and (3) second-stage roasting: the heating rate is 50-200 ℃/h, and the roasting is carried out for 1-4 h at the constant temperature of 350-500 ℃.

8. The preparation method of the animal and vegetable oil hydrogenation direct deoxidation catalyst according to the claim 1 is characterized in that: in the S5, the metal salt solution contains a VIB group metal compound and a VIII group metal compound, the metal in the VIB group metal compound is cobalt or nickel, and the NiO content is 1-10% by taking the weight of the catalyst as a reference; the metal in the VIII family metal compound is molybdenum or tungsten, and the content of WO3 is 15-50% by weight of the catalyst; the curing temperature is 25-28 ℃, and the curing time is 4-48 h; the drying temperature is 70-150 ℃, and the drying time is 2-6 h; the three-stage roasting is carried out, wherein the first-stage roasting is carried out for 0.5h-2h at the constant temperature of 200-230 ℃, the second-stage roasting is carried out for 0.5h-2h at the constant temperature of 300-360 ℃, and the third-stage roasting is finally carried out for 2h-4h at the constant temperature of 450-500 ℃.

Technical Field

The invention relates to the technical field of inorganic material preparation, in particular to a preparation method of a catalyst for directly deoxidizing animal and vegetable oil by hydrogenation.

Background

The kitchen waste grease is a general concept and mainly refers to waste animal grease and swill oil which are repeatedly heated for use and waste oil collected from a sewer of a catering enterprise. The main components of the kitchen waste grease are fatty acid, fatty dilute acid, fatty diacid and ester, and simultaneously contain a large amount of bacteria and other harmful chemical substances, so that the direct discharge can pollute soil and rivers, and simultaneously can cause a large amount of waste of resources. The comprehensive utilization of the kitchen waste grease mainly comprises 3 types: the kitchen waste grease is used for preparing alternative fatty acid and sodium fatty acid, and the technology degrades the kitchen waste grease, separates the kitchen waste grease to obtain higher fatty acid which can be used as a mineral separation collector, thereby avoiding environmental pollution and reducing food safety threat; the method is characterized by producing biodiesel by using kitchen waste oil, and the technology is based on ester exchange reaction, uses the kitchen waste oil and methanol as raw materials, and generates fatty acid methyl ester under the action of a catalyst; the technology is used for producing ethanol and methane by using kitchen waste oil, and the oil is refined and purified into biodiesel by the technology, and then is converted into fuel ethanol and methane by the processes of enzymolysis, anaerobic fermentation and the like. The waste palm oil is particularly waste palm oil produced in the refining deacidification process in the palm oil production process, and the main components of the waste palm oil are fatty acid and fatty dilute acid. The acid value is high, generally more than 150mgKOH/g, the viscosity is high, the contents of sulfur, nitrogen and metal are high, and the recycling and reprocessing difficulty is high.

At present, the hydrogenation deoxidation reaction mainly occurs in the hydrogenation reaction of the kitchen waste grease and the waste palm oil, the hydrogenation deoxidation reaction has three types, namely hydrogenation direct deoxidation, hydrogenation decarbonylation and hydrogenation decarboxylation reaction, the fatty acid hydrogenation direct deoxidation reaction correspondingly generates alkane with corresponding carbon number, the fatty acid hydrogenation decarbonylation reaction or hydrogenation decarboxylation reaction correspondingly generates alkane with one less carbon number, and CO are generated₂A gas. The hydrogenation decarbonylation reaction and the hydrogenation decarboxylation reaction not only reduce the yield of the product liquid, but also produce CO and CO₂The gas is difficult to remove in the industrial production process, and the difficulty of the purification of the recycle hydrogen and the production and investment cost are increased. Therefore, a preparation method of the direct deoxidation catalyst for animal and vegetable oil hydrogenation is provided.

Disclosure of Invention

The invention aims to provide a preparation method of a direct deoxidation catalyst for animal and vegetable oil hydrogenation, which aims to solve the problems in the background technology.

In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a catalyst for directly deoxidizing animal and vegetable oil by hydrogenation comprises the following steps:

s1, stirring the SB powder and water uniformly, adding a peptizing agent, and stirring uniformly to form an adhesive;

s2, mixing the pseudo-boehmite and sesbania powder uniformly in a rolling machine, adding water, adding the adhesive prepared in S1, and stirring uniformly to prepare a material before forming, wherein the pseudo-boehmite contains silicon dioxide, and the sesbania powder contains aluminum oxide;

s3, extruding the forming material in the S2 on a strip extruding machine for forming, curing, drying and roasting to obtain a catalyst carrier;

s4, pre-impregnating the catalyst carrier in the S3 with an auxiliary agent solution at a certain temperature, and carrying out health preserving, drying and secondary roasting to obtain an auxiliary agent-containing carrier;

and S5, impregnating the assistant-containing carrier in the S4 with a metal salt solution, and carrying out health preserving, drying and three-stage roasting to obtain the catalyst.

As further preferable in the present technical solution: the mass ratio of the SB powder to the water is 0.15:1-0.6: 1.

As further preferable in the present technical solution: the peptizing agent is a mixture of organic acid or inorganic acid and water, the mass ratio of the organic acid or the inorganic acid to the water in the peptizing agent is 0.015:1-0.65:1, and the mass ratio of the peptizing agent to the SB powder is 0.05:1-0.1: 1.

As further preferable in the present technical solution: the content of silicon dioxide in the pseudo-boehmite is 1% -30%, and the adding amount of aluminum oxide in the sesbania powder is 3%; the mass ratio of the adhesive to the alumina in the pseudo-boehmite is 1.5:1-3: 1.

As further preferable in the present technical solution: when the pseudo-boehmite is mixed with the sesbania powder, water is added, and the water addition amount is 10-80% of the content of alumina in the pseudo-boehmite.

As further preferable in the present technical solution: in the S3, in the curing process, the curing temperature of the additive-containing carrier is 25-28 ℃ at room temperature for 4-48 h; the drying temperature is 70-150 ℃, and the drying time is 2-6 h; the heating rate of the roasting condition is 50-200 ℃/h, the roasting temperature is 400-600-.

As further preferable in the present technical solution: in the S4, the auxiliary agent is phosphide such as phosphoric acid, phosphorous acid, ammonium phosphate, diammonium hydrogen phosphate or ammonium dihydrogen phosphate, the impregnation amount of phosphorus is 0.2-8% of the catalyst carrier, a saturated impregnation mode is adopted, the solution temperature of the auxiliary agent is 25-70 ℃, the curing temperature of the auxiliary agent-containing carrier is 25-28 ℃, and the curing time is 4-48 hours; the drying temperature is 70-150 ℃, and the drying time is 2-6 h; the second-stage roasting comprises two times of roasting, wherein in the first-stage roasting, the roasting is carried out from room temperature 25 ℃ to 200-230 ℃, the heating rate is 30-200 ℃/h, and the constant-temperature roasting is carried out for 0.5-2 h; and (3) second-stage roasting: the heating rate is 50-200 ℃/h, and the roasting is carried out for 1-4 h at the constant temperature of 350-500 ℃.

As further preferable in the present technical solution: in the S5, the metal salt solution contains a VIB group metal compound and a VIII group metal compound, the metal in the VIB group metal compound is cobalt or nickel, and the NiO content is 1-10% by taking the weight of the catalyst as a reference; the metal in the VIII family metal compound is molybdenum or tungsten, and the content of WO3 is 15-50% by weight of the catalyst; the curing temperature is 25-28 ℃, and the curing time is 4-48 h; the drying temperature is 70-150 ℃, and the drying time is 2-6 h; the three-stage roasting is carried out, wherein the first-stage roasting is carried out for 0.5h-2h at the constant temperature of 200-230 ℃, the second-stage roasting is carried out for 0.5h-2h at the constant temperature of 300-360 ℃, and the third-stage roasting is finally carried out for 2h-4h at the constant temperature of 450-500 ℃.

Compared with the prior art, the invention has the beneficial effects that: the invention can pre-soak phosphorus, can expand pores, is beneficial to the diffusion of macromolecular grease, adopts a two-stage roasting process to improve the dispersion degree of the phosphorus in a carrier, and after the phosphorus is soaked by metal components, the metal components are uniformly contacted with an auxiliary agent, after three-stage roasting, the dispersion degree of the metal components is improved, the synergistic effect of the auxiliary agents of silicon and phosphorus and the metal active components is exerted to the maximum extent, meanwhile, the presoaking of the auxiliary agent phosphorus achieves the effect of regulating the pore structure, the catalyst is particularly suitable for the direct deoxidation reaction of the hydrogenation of the macromolecules of the animal and vegetable oil esters, the catalyst prepared by the invention not only improves the external specific surface area of the formed carrier, meanwhile, the loading capacity and the dispersion degree of the active metal on the surface of the carrier can be improved, the synergistic effect of the auxiliary agents of silicon and phosphorus and the active metal is improved, the difficulty of the purification of the circulating hydrogen and the production and investment costs are reduced, and the catalyst is particularly suitable for the direct deoxidation reaction of the hydrogenation of the macromolecules of the animal and vegetable oil esters.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the data tables in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

TABLE 1 physicochemical Properties of the catalyst

Evaluation of catalyst:

the mixed oil of the palmitic acid and the kitchen waste grease is used for producing the liquid paraffin on a laboratory pilot-scale reaction device. The raw materials are shown in Table 2.

TABLE 2 blend oil Properties

The test relates to a series reaction of two reactors, raw oil and hydrogen are mixed and then enter a first reactor to mainly carry out olefin saturation reaction, in particular to easily coked diolefins; the raw oil continuously enters a second reactor to mainly carry out hydrodeoxygenation, desulfurization and denitrification reactions. The catalyst volume ratio of the two reactors was 1: 2. The process conditions and the product yield are shown in Table 3.

The catalyst used in the first reactor contains an alumina carrier, nickel and molybdenum hydrogenation active metal components, and by taking the catalyst as a reference, the content of nickel oxide is 1% -5%, and the content of molybdenum trioxide is 5% -20%.

The catalyst used in the second reactor is the catalyst prepared by the invention.

TABLE 3 Process conditions and product yields

As can be seen from the activity comparison tests in Table 3, in the hydrodeoxygenation process of the kitchen waste oil and the palmitic acid mixed oil, the catalyst mainly performs a hydrogenation direct deoxygenation reaction, so that the product yield is high, and less CO and CO are generated₂Gas, while more decarbonylation and decarboxylation occurred with the comparative catalyst, more CO and CO were produced₂Gas, and low product yield. More CO and CO in the circulating hydrogen in the industrial production process₂Too high a gas concentration not only affects catalyst performance and reduces hydrogen purity, but also increases hydrogen purificationThe equipment investment cost is increased.

Table 4 shows the properties of the liquid paraffin produced by using the catalyst of the present invention.

TABLE 4C⁵⁺Composition Properties

As can be seen from Table 4, C is obtained after the mixed oil of the kitchen waste oil and the palmitic acid is subjected to hydrodeoxygenation by using the catalyst of the invention⁵⁺The product meets the Class B product index requirement of EN 15940:2016 index requirement.