阅读说明：本技术 生物柴油加氢脱氧-异构化催化剂及其制备方法和应用 (Biodiesel hydrodeoxygenation-isomerization catalyst and preparation method and application thereof ) 是由 陈钦 李明时 张伟 张旭中 于 2021-08-18 设计创作，主要内容包括：本发明公开了生物柴油加氢脱氧-异构化催化剂及其制备方法和应用,制备方法包括将铝源、磷源和硅源分散于去离子水中,令其形成凝胶态混合物,然后再加入镍源并使其分散在凝胶态混合物中,继而将混合物料置于反应釜中,然后再将模板剂和扩孔剂以及去离子水加入到混合物料中,并在搅拌混合后,对混合物料进行干燥、晶化处理,再将反应体系温度升温至610～650℃进行焙烧处理5～7h,制得掺杂有镍的SAPO-11载体；再将SAPO-11载体、拟薄水铝石、田菁粉和乙酸溶液进行混合后,经研磨、搅拌、挤出成型和干燥后,制成催化剂前驱体；最后将催化剂前驱体置于还原气体氛围下进行还原反应处理,再经磷化处理后,制得催化剂；本方案工艺稳定可靠、成本低且产品性能稳定。(The invention discloses a biodiesel hydrodeoxygenation-isomerization catalyst and a preparation method and application thereof, wherein the preparation method comprises the steps of dispersing an aluminum source, a phosphorus source and a silicon source in deionized water to form a gel-state mixture, then adding a nickel source and dispersing the nickel source in the gel-state mixture, then placing the mixed material in a reaction kettle, then adding a template agent, a pore-expanding agent and deionized water into the mixed material, stirring and mixing, drying and crystallizing the mixed material, heating the reaction system to 610-650 ℃ to perform roasting treatment for 5-7 hours, and preparing a nickel-doped SAPO-11 carrier; mixing the SAPO-11 carrier, the pseudo-boehmite, the sesbania powder and the acetic acid solution, grinding, stirring, extruding, forming and drying to prepare a catalyst precursor; finally, placing the catalyst precursor in a reducing gas atmosphere for reduction reaction treatment, and then carrying out phosphating treatment to obtain the catalyst; the technical scheme has stable and reliable process, low cost and stable product performance.)

1. The preparation method of the biodiesel hydrodeoxygenation-isomerization catalyst is characterized by comprising the following steps: it includes: dispersing an aluminum source, a phosphorus source and a silicon source in deionized water to form a gel-state mixture, then adding a nickel source and dispersing the nickel source in the gel-state mixture, then placing the mixed material in a reaction kettle, then adding a template agent, a pore-expanding agent and deionized water into the mixed material, stirring and mixing, drying and crystallizing the mixed material, heating the reaction system to 610-650 ℃, and roasting for 5-7 h to obtain a nickel-doped SAPO-11 carrier; mixing the SAPO-11 carrier, the pseudo-boehmite, the sesbania powder and the acetic acid solution, grinding, stirring, extruding, forming and drying to prepare a catalyst precursor; and finally, placing the catalyst precursor in a reducing gas atmosphere for reduction reaction treatment, and then carrying out phosphating treatment to obtain the catalyst.

2. The method of preparing a biodiesel hydrodeoxygenation-isomerization catalyst of claim 1, characterized in that: the method comprises the following specific steps:

s01, dispersing an aluminum source, a phosphorus source and a silicon source in deionized water, adjusting the pH value of the mixed solution to 3-4 to enable the mixed solution to form a gel-state mixture, and then adding a nickel source and dispersing the nickel source in the gel-state mixture to obtain a mixed material;

s02, placing the mixed material into a reaction kettle, pre-mixing a template agent, a pore-expanding agent and deionized water, adding the mixed material into the reaction kettle, stirring and mixing, placing the mixed material into an environment of 90-95 ℃ for drying treatment for 0.5-1 h, adjusting the temperature of the reaction kettle to 120-145 ℃ for crystallization treatment for 12-20 h, and finally heating the temperature of a reaction system to 610-650 ℃ for roasting treatment for 5-7 h to prepare the nickel-doped SAPO-11 carrier;

s03, mixing the SAPO-11 carrier, the pseudo-boehmite, the sesbania powder and the acetic acid solution, grinding, stirring, extruding and molding, and drying at 105-115 ℃ for 1-3 h to prepare a catalyst precursor;

s04, placing the catalyst precursor in a hydrogen atmosphere at a temperature of 400-440 ℃, carrying out reduction reaction for 3.5-5 h, then reducing the temperature of the system to 120-140 ℃, then introducing a phosphating solution for soaking, then heating the temperature of the system to 220-240 ℃ at a heating rate of 2-4 ℃/min, keeping the temperature for 2.5-3 h, then heating the temperature of the system to 360-380 ℃ at a heating rate of 2-4 ℃/min, keeping the temperature for 2.5-3 h, discharging the phosphating solution, simultaneously inputting normal-temperature inert gas for drying and auxiliary cooling, and obtaining the catalyst after the temperature of the system is restored to normal temperature.

3. The method of preparing a biodiesel hydrodeoxygenation-isomerization catalyst according to claim 2, characterized in that: in the step S01, the adding molar ratio of the aluminum source, the phosphorus source, the silicon source, the deionized water and the nickel source is 1: 1-1.5: 0.2-0.6: 40-60: 0.4-0.8;

in the step S02, the adding molar ratio of the template agent to the pore-expanding agent to the deionized water is 2-5: 0.2-0.8: 5-10;

in the step S02, the adding molar ratio of the components of aluminum source, phosphorus source, silicon source, deionized water, nickel source, template agent and pore-expanding agent in the reaction kettle is 1: 1-1.5: 0.2-0.6: 45-70: 0.4-0.8: 2-5: 0.2-0.8;

in the step S03, the mixing mass ratio of the SAPO-11 carrier, the pseudo-boehmite and the sesbania powder is 70-80: 12-18: 3-4;

wherein the mass concentration of the acetic acid solution is 30-35%, and the addition amount of the acetic acid solution is 3-8% of the mass of the SAPO-11 carrier.

4. The method of preparing a biodiesel hydrodeoxygenation-isomerization catalyst according to claim 2, characterized in that: in step S04, after the phosphating solution is introduced, the circulation of the phosphating solution is maintained at a flow rate of 0.5 to 1.5 m/min.

5. The method of preparing a biodiesel hydrodeoxygenation-isomerization catalyst of claim 3, characterized in that: in step S02, the adding molar ratio of the components of aluminum source, phosphorus source, silicon source, deionized water, nickel source, template agent and pore-expanding agent in the reaction kettle is 1: 1.3: 0.4: 60: 0.6: 3.5: 0.6;

wherein the mass concentration of the acetic acid solution is 35 percent, and the adding amount of the acetic acid solution is 6 percent of the mass of the SAPO-11 carrier.

6. The method of preparing a biodiesel hydrodeoxygenation-isomerization catalyst according to claim 2, characterized in that: in step S03, the mixing mass ratio of the SAPO-11 carrier, the pseudo-boehmite and the sesbania powder is 75: 14: 3.5.

7. The process for the preparation of a hydrodeoxygenation-isomerization catalyst for biodiesel according to any one of claims 2 to 6, characterized in that: the aluminum source is more than one of aluminum hydroxide, aluminum isopropoxide, pseudo-boehmite and aluminum nitrate;

the phosphorus source is phosphoric acid solution;

the silicon source is more than one of silica gel, silica sol and tetraethoxysilane;

the nickel source is basic nickel carbonate;

the template agent is one of dodecyl dimethyl tertiary amine, polyvinylpyrrolidone, hexadecyl trimethyl ammonium bromide or dodecyl sodium sulfate;

the pore-expanding agent is n-butyl alcohol;

the phosphating solution is an n-heptane solution of triphenylphosphine, wherein the mass concentration of the triphenylphosphine is 3% -4%, and the liquid volume airspeed is 2-3 h^-1。

8. A hydrodeoxygenation-isomerization catalyst for biodiesel, which is characterized in that: the preparation method of any one of claims 1 to 7, wherein the active component attached to the SAPO-11 carrier is nickel phosphide, and the loading amount of the nickel phosphide accounts for 10-15% of the mass of the catalyst.

9. The use of the biodiesel hydrodeoxygenation-isomerization catalyst in catalyzing the hydrodeoxygenation-isomerization of fatty acid methyl esters to prepare isoparaffins according to claim 8, wherein the biodiesel comprises the following components in percentage by weight: the application method comprises the following steps:

(1) loading the biodiesel hydrodeoxygenation-isomerization catalyst into a reactor;

(2) pumping fatty acid methyl ester into a reactor at a preset temperature of 265-275 ℃ and a preset hydrogen pressure of 4.0-5.0 Mpa, and carrying out hydrodeoxygenation-isomerization reaction on the fatty acid methyl ester to obtain normal paraffin and isoparaffin with the same length as the fatty acid carbon chain in the fatty acid methyl ester.

10. The use of the biodiesel hydrodeoxygenation-isomerization catalyst in catalyzing the hydrodeoxygenation-isomerization of fatty acid methyl esters to prepare isoparaffins according to claim 9, wherein the biodiesel comprises the following components: the carbon chain length of fatty acid in the fatty acid methyl ester is 16-22, the volume ratio of hydrogen to the fatty acid methyl ester is 650-750, the introducing pressure is 4.4-4.5 Mpa, and the temperature in the reactor is 268-272 ℃.

Technical Field

The invention relates to the technical field of catalysts, in particular to a hydrodeoxygenation-isomerization catalyst for biodiesel as well as a preparation method and application thereof.

Background

Biodiesel, which is an energy source that is popular in the time, is widely regarded as one of supplementary energy sources for fossil energy because of its advantages of being environmentally friendly and renewable. Since the main chemical composition of biodiesel is fatty acid methyl ester, it is usually made by transesterification of vegetable fats and oils (fatty acid triglycerides) with methanol. Biodiesel has relatively high condensation point and cloud point, and has poor chemical stability, high oxygen content and low energy density, so that the biodiesel is difficult to be completely compatible with traditional fossil diesel, thereby limiting the application of the biodiesel. Based on the above, the conversion of fatty acid methyl ester into bio-based alkane which is similar to the components of the traditional fossil diesel and has good compatibility through hydrodeoxygenation is a problem with positive practical significance.

Disclosure of Invention

Aiming at the situation of the prior art, the invention aims to provide a biodiesel hydrodeoxygenation-isomerization catalyst which is stable and reliable in process, low in cost and stable in product performance, and a preparation method and application thereof.

In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:

a method for preparing a biodiesel hydrodeoxygenation-isomerization catalyst, comprising: dispersing an aluminum source, a phosphorus source and a silicon source in deionized water to form a gel-state mixture, then adding a nickel source and dispersing the nickel source in the gel-state mixture, then placing the mixed material in a reaction kettle, then adding a template agent, a pore-expanding agent and deionized water into the mixed material, stirring and mixing, drying and crystallizing the mixed material, heating the reaction system to 610-650 ℃, and roasting for 5-7 h to obtain a nickel-doped SAPO-11 carrier; mixing the SAPO-11 carrier, the pseudo-boehmite, the sesbania powder and the acetic acid solution, grinding, stirring, extruding, forming and drying to prepare a catalyst precursor; and finally, placing the catalyst precursor in a reducing gas atmosphere for reduction reaction treatment, and then carrying out phosphating treatment to obtain the catalyst.

As a possible implementation manner, further, the scheme includes the following specific steps:

s01, dispersing an aluminum source, a phosphorus source and a silicon source in deionized water, adjusting the pH value of the mixed solution to 3-4 to enable the mixed solution to form a gel-state mixture, and then adding a nickel source and dispersing the nickel source in the gel-state mixture to obtain a mixed material;

s02, placing the mixed material into a reaction kettle, pre-mixing a template agent, a pore-expanding agent and deionized water, adding the mixed material into the reaction kettle, stirring and mixing, placing the mixed material into an environment of 90-95 ℃ for drying treatment for 0.5-1 h, adjusting the temperature of the reaction kettle to 120-145 ℃ for crystallization treatment for 12-20 h, and finally heating the temperature of a reaction system to 610-650 ℃ for roasting treatment for 5-7 h to prepare the nickel-doped SAPO-11 carrier;

s03, mixing the SAPO-11 carrier, the pseudo-boehmite, the sesbania powder and the acetic acid solution, grinding, stirring, extruding and molding, and drying at 105-115 ℃ for 1-3 h to prepare a catalyst precursor;

s04, placing the catalyst precursor in a hydrogen atmosphere at a temperature of 400-440 ℃, carrying out reduction reaction for 3.5-5 h, then reducing the temperature of the system to 120-140 ℃, then introducing a phosphating solution for soaking, then heating the temperature of the system to 220-240 ℃ at a heating rate of 2-4 ℃/min, keeping the temperature for 2.5-3 h, then heating the temperature of the system to 360-380 ℃ at a heating rate of 2-4 ℃/min, keeping the temperature for 2.5-3 h, discharging the phosphating solution, simultaneously inputting normal-temperature inert gas for drying and auxiliary cooling, and obtaining the catalyst after the temperature of the system is restored to normal temperature.

Preferably, in step S01, the adding molar ratio of the aluminum source, the phosphorus source, the silicon source, the deionized water and the nickel source is 1: 1-1.5: 0.2-0.6: 40-60: 0.4-0.8;

in the step S02, the adding molar ratio of the template agent to the pore-expanding agent to the deionized water is 2-5: 0.2-0.8: 5-10;

in the step S02, the adding molar ratio of the components of aluminum source, phosphorus source, silicon source, deionized water, nickel source, template agent and pore-expanding agent in the reaction kettle is 1: 1-1.5: 0.2-0.6: 45-70: 0.4-0.8: 2-5: 0.2-0.8;

in the step S03, the mixing mass ratio of the SAPO-11 carrier, the pseudo-boehmite and the sesbania powder is 70-80: 12-18: 3-4;

wherein the mass concentration of the acetic acid solution is 30-35%, and the addition amount of the acetic acid solution is 3-8% of the mass of the SAPO-11 carrier.

As a preferable embodiment, it is preferable that the phosphating solution is circulated at a flow rate of 0.5 to 1.5m/min after the introduction of the phosphating solution in step S04.

As a preferred implementation option, preferably, in step S02, the aluminum source, the phosphorus source, the silicon source, the deionized water, the nickel source, the template agent and the pore-expanding agent are added in a molar ratio of 1: 1.3: 0.4: 60: 0.6: 3.5: 0.6 in the reaction kettle;

wherein the mass concentration of the acetic acid solution is 35 percent, and the adding amount of the acetic acid solution is 6 percent of the mass of the SAPO-11 carrier.

As a preferable implementation option, in step S03, the mixing mass ratio of the SAPO-11 carrier, the pseudoboehmite and the sesbania powder is 75: 14: 3.5.

As a preferred implementation choice, the aluminum source is preferably one or more of aluminum hydroxide, aluminum isopropoxide, pseudoboehmite, and aluminum nitrate;

the phosphorus source is phosphoric acid solution;

the silicon source is more than one of silica gel, silica sol and tetraethoxysilane;

the nickel source is basic nickel carbonate;

the template agent is one of dodecyl dimethyl tertiary amine, polyvinylpyrrolidone, hexadecyl trimethyl ammonium bromide or dodecyl sodium sulfate;

the pore-expanding agent is n-butyl alcohol;

the phosphating solution is an n-heptane solution of triphenylphosphine, wherein the mass concentration of the triphenylphosphine is 3% -4%, and the liquid volume airspeed is 2-3 h^-1。

Based on the preparation method, the invention also provides a biodiesel hydrodeoxygenation-isomerization catalyst which is prepared by the preparation method, wherein the active component attached to the SAPO-11 carrier is nickel phosphide, and the nickel phosphide loading accounts for 10-15% of the catalyst by mass.

Based on the catalyst scheme, the invention also provides an application of the biodiesel hydrodeoxygenation-isomerization catalyst in catalyzing hydrodeoxygenation-isomerization of fatty acid methyl ester to prepare isoparaffin, and the application method comprises the following steps:

(1) loading the biodiesel hydrodeoxygenation-isomerization catalyst into a reactor;

(2) pumping fatty acid methyl ester into a reactor at a preset temperature of 265-275 ℃ and a preset hydrogen pressure of 4.0-5.0 Mpa, and carrying out hydrodeoxygenation-isomerization reaction on the fatty acid methyl ester to obtain normal paraffin and isoparaffin with the same length as the fatty acid carbon chain in the fatty acid methyl ester.

As a preferred implementation choice, the carbon chain length of the fatty acid in the fatty acid methyl ester is 16-22, the volume ratio of the hydrogen to the fatty acid methyl ester is 650-750, the introducing pressure is 4.4-4.5 Mpa, and the temperature in the reactor is 268-272 ℃.

By adopting the technical scheme, compared with the prior art, the invention has the beneficial effects that: the method has the advantages that a nickel source is doped in a gel-state mixture (non-stable gel) prepared by mixing an aluminum source, a phosphorus source, a silicon source and deionized water, so that the nickel source has high dispersion stability and diffusivity during doping and dispersion, then a nickel-doped SAPO-11 carrier is prepared by crystallization and roasting, a catalyst precursor is prepared by mixing the nickel-doped SAPO-11 carrier with pseudo-boehmite, sesbania powder and acetic acid, the catalyst precursor is placed in phosphating solution for high-temperature treatment to prepare a catalyst loaded with nickel phosphide as an active ingredient, and when the phosphating solution and the catalyst precursor are immersed, the phosphating solution exists in a low-speed flowing state, so that the diffusibility of the nickel phosphide in the catalyst precursor can be improved, and meanwhile, the nickel source in the catalyst precursor is favorably and fully contacted with phosphorus in the phosphating solution, the yield of the nickel phosphide loaded on the catalyst is higher, and the catalytic capability and the service life of the catalyst are better.

Drawings

The invention will be further explained with reference to the drawings and the detailed description below:

FIG. 1 is a schematic flow chart of the preparation method of the present invention.

Detailed Description

As shown in figure 1, the preparation method of the hydrodeoxygenation-isomerization catalyst for biodiesel comprises the following specific steps:

s01, dispersing an aluminum source, a phosphorus source and a silicon source in deionized water, adjusting the pH value of the mixed solution to 3-4 to enable the mixed solution to form a gel-state mixture, and then adding a nickel source and dispersing the nickel source in the gel-state mixture to obtain a mixed material;

s02, placing the mixed material into a reaction kettle, pre-mixing a template agent, a pore-expanding agent and deionized water, adding the mixed material into the reaction kettle, stirring and mixing, placing the mixed material into an environment of 90-95 ℃ for drying treatment for 0.5-1 h, adjusting the temperature of the reaction kettle to 120-145 ℃ for crystallization treatment for 12-20 h, and finally heating the temperature of a reaction system to 610-650 ℃ for roasting treatment for 5-7 h to prepare the nickel-doped SAPO-11 carrier;

s03, mixing the SAPO-11 carrier, the pseudo-boehmite, the sesbania powder and the acetic acid solution, grinding, stirring, extruding and molding, and drying at 105-115 ℃ for 1-3 h to prepare a catalyst precursor;

s04, placing the catalyst precursor in a hydrogen atmosphere at a temperature of 400-440 ℃, carrying out reduction reaction for 3.5-5 h, then reducing the temperature of the system to 120-140 ℃, then introducing a phosphating solution for soaking, then heating the temperature of the system to 220-240 ℃ at a heating rate of 2-4 ℃/min, keeping the temperature for 2.5-3 h, then heating the temperature of the system to 360-380 ℃ at a heating rate of 2-4 ℃/min, keeping the temperature for 2.5-3 h, discharging the phosphating solution, simultaneously inputting normal-temperature inert gas for drying and auxiliary cooling, and obtaining the catalyst after the temperature of the system is restored to normal temperature.

In the step S01, the adding molar ratio of the aluminum source, the phosphorus source, the silicon source, the deionized water and the nickel source is 1: 1-1.5: 0.2-0.6: 40-60: 0.4-0.8; in the step S02, the adding molar ratio of the template agent to the pore-expanding agent to the deionized water is 2-5: 0.2-0.8: 5-10; in the step S02, the adding molar ratio of the components of aluminum source, phosphorus source, silicon source, deionized water, nickel source, template agent and pore-expanding agent in the reaction kettle is 1: 1-1.5: 0.2-0.6: 45-70: 0.4-0.8: 2-5: 0.2-0.8; preferably, the adding molar ratio of the components of aluminum source, phosphorus source, silicon source, deionized water, nickel source, template agent and pore-expanding agent in the reaction kettle is 1: 1.3: 0.4: 60: 0.6: 3.5: 0.6.

In the step S03, the mixing mass ratio of the SAPO-11 carrier, the pseudo-boehmite and the sesbania powder is 70-80: 12-18: 3-4; preferably, in step S03, the mixing mass ratio of the SAPO-11 carrier, the pseudo-boehmite and the sesbania powder is 75: 14: 3.5; the mass concentration of the acetic acid solution is 30-35%, and the addition amount of the acetic acid solution is 3% -8% of the mass of the SAPO-11 carrier; preferably, the mass concentration of the acetic acid solution is 35%, and the addition amount of the acetic acid solution is 6% of the mass of the SAPO-11 carrier.

In this embodiment, as a preferred embodiment, it is preferable that the phosphating solution is circulated at a flow rate of 0.5 to 1.5m/min after being introduced in step S04.

In the scheme, the aluminum source is more than one of aluminum hydroxide, aluminum isopropoxide, pseudo-boehmite and aluminum nitrate;

the phosphorus source is phosphoric acid solution;

the silicon source is more than one of silica gel, silica sol and tetraethoxysilane;

the nickel source is basic nickel carbonate;

the template agent is one of dodecyl dimethyl tertiary amine, polyvinylpyrrolidone, hexadecyl trimethyl ammonium bromide or dodecyl sodium sulfate;

the pore-expanding agent is n-butyl alcohol;

the phosphating solution is an n-heptane solution of triphenylphosphine, wherein the mass concentration of the triphenylphosphine is 3% -4%, and the liquid volume airspeed is 2-3 h^-1。

Based on the preparation method, the invention also provides a biodiesel hydrodeoxygenation-isomerization catalyst which is prepared by the preparation method, wherein the active component attached to the SAPO-11 carrier is nickel phosphide, and the nickel phosphide loading accounts for 10-15% of the catalyst by mass.

Based on the catalyst scheme, the invention also provides an application of the biodiesel hydrodeoxygenation-isomerization catalyst in catalyzing hydrodeoxygenation-isomerization of fatty acid methyl ester to prepare isoparaffin, and the application method comprises the following steps:

(1) loading the biodiesel hydrodeoxygenation-isomerization catalyst into a reactor;

(2) pumping fatty acid methyl ester into a reactor at a preset temperature of 265-275 ℃ and a preset hydrogen pressure of 4.0-5.0 Mpa, and carrying out hydrodeoxygenation-isomerization reaction on the fatty acid methyl ester to obtain normal paraffin and isoparaffin with the same length as the fatty acid carbon chain in the fatty acid methyl ester.

As a preferred implementation choice, the carbon chain length of the fatty acid in the fatty acid methyl ester is 16-22, the volume ratio of the hydrogen to the fatty acid methyl ester is 650-750, the introducing pressure is 4.4-4.5 Mpa, and the temperature in the reactor is 268-272 ℃.

The scheme of the invention is further described by combining a plurality of embodiments and test examples as follows:

example 1

The preparation method of the biodiesel hydrodeoxygenation-isomerization catalyst comprises the following specific steps:

s01, dispersing an aluminum source, a phosphorus source and a silicon source in deionized water, adjusting the pH value of the mixed solution to 3-4 to enable the mixed solution to form a gel-state mixture, and then adding a nickel source and dispersing the nickel source in the gel-state mixture to obtain a mixed material;

s02, placing the mixed material into a reaction kettle, pre-mixing a template agent, a pore-expanding agent and deionized water, adding the mixed material into the reaction kettle, stirring and mixing the mixed material, placing the mixed material into an environment of 90-95 ℃ for drying treatment for 1h, adjusting the temperature of the reaction kettle to 130-135 ℃ for crystallization treatment for 16h, and finally heating the temperature of a reaction system to 620-630 ℃ for roasting treatment for 6h to prepare the nickel-doped SAPO-11 carrier;

s03, mixing the SAPO-11 carrier, the pseudo-boehmite, the sesbania powder and the acetic acid solution, grinding, stirring, extruding and molding, and drying at 110 +/-2 ℃ for 2 hours to prepare a catalyst precursor;

s04, placing the catalyst precursor in a hydrogen atmosphere at a temperature of 420-430 ℃ for reduction reaction for 4h, then reducing the temperature of the system to 130 +/-5 ℃, then introducing phosphating solution for soaking, then heating the temperature of the system to 230 +/-5 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 3h, then heating the temperature of the system to 370 +/-5 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 3h, discharging the phosphating solution, simultaneously inputting normal-temperature inert gas for drying and auxiliary cooling, and obtaining the catalyst after the temperature of the system is restored to normal temperature.

In step S01 of this embodiment, the adding molar ratio of the aluminum source, the phosphorus source, the silicon source, the deionized water and the nickel source is 1: 0.2: 40: 0.4; in step S02, the adding molar ratio of the template agent, the pore-expanding agent and the deionized water is 2: 0.2: 5; in step S02, the molar ratio of aluminum source, phosphorus source, silicon source, deionized water, nickel source, template agent and pore-enlarging agent in the reaction kettle is 1: 0.2: 45: 0.4: 2: 0.2.

In step S03 of this embodiment, the mixing mass ratio of the SAPO-11 carrier, the pseudo-boehmite, and the sesbania powder is 70: 12: 3; the mass concentration of the acetic acid solution is 30%, and the addition amount of the acetic acid solution is 3% of the mass of the SAPO-11 carrier.

In this embodiment, the aluminum source is aluminum hydroxide; the phosphorus source is phosphoric acid solution; the silicon source is tetraethoxysilane; what is needed isThe nickel source is basic nickel carbonate; the template agent is dodecyl dimethyl tertiary amine; the pore-expanding agent is n-butyl alcohol; the phosphating solution is an n-heptane solution of triphenylphosphine, wherein the mass concentration of the triphenylphosphine is 3 percent, and the liquid volume space velocity is 2.5h^-1。

Performance testing

The mass percent of nickel in the catalyst prepared in the embodiment is about 8.9% by adopting ICP (inductively coupled plasma) spectrometry, and then XRD (X-ray diffraction) is used for representing the state of the nickel in the catalyst, so that the nickel is mainly in the form of nickel phosphide; the mass fraction of the nickel phosphide in the catalyst is calculated by adopting the following calculation method:

w＝x×w1/(m1/m2)＝0.95×8.9％/(28×2/(28×2+15))＝10.7％；

wherein, w is the mass percentage of the nickel phosphide in the catalyst; x is a correction coefficient set to 0.95; m1 is the relative atomic mass of nickel in the nickel phosphide; m2 is the relative molecular mass of the nickel phosphide.

Example 2

This example is substantially the same as example 1, except that in step S01, the molar ratio of aluminum source, phosphorus source, silicon source, deionized water, and nickel source is 1: 1.3: 0.4: 50: 0.6; in step S02, the addition molar ratio of the template agent, the pore-expanding agent and the deionized water is 3.5: 0.6: 10.

Wherein, the adding mol ratio of the components of the aluminum source, the phosphorus source, the silicon source, the deionized water, the nickel source, the template agent and the pore-expanding agent in the reaction kettle of the step S02 is 1: 1.3: 0.4: 60: 0.6: 3.5: 0.6; in step S03, the mixing mass ratio of the SAPO-11 carrier, the pseudo-boehmite and the sesbania powder is 75: 14: 3.5, the mass concentration of the acetic acid solution is 35%, and the adding amount of the acetic acid solution is 6% of the mass of the SAPO-11 carrier.

The parameters of the other steps in this embodiment are the same as those in embodiment 1, and are not described again.

Performance testing

The mass percent of nickel in the catalyst prepared in the embodiment is about 11.2% by adopting ICP (inductively coupled plasma) spectrometry, and then XRD (X-ray diffraction) is used for representing the state of the nickel in the catalyst, so that the nickel is mainly in the form of nickel phosphide; the mass fraction of the nickel phosphide in the catalyst is calculated by adopting the following calculation method:

w＝x×w1/(m1/m2)＝0.95×11.2％/(28×2/(28×2+15))＝13.5％；

wherein, w is the mass percentage of the nickel phosphide in the catalyst; x is a correction coefficient set to 0.95; m1 is the relative atomic mass of nickel in the nickel phosphide; m2 is the relative molecular mass of the nickel phosphide.

Example 3

This example is substantially the same as example 1, except that in step S01, the molar ratio of aluminum source, phosphorus source, silicon source, deionized water, and nickel source is 1: 1.5: 0.6: 60: 0.8; in step S02, the addition molar ratio of the template agent, the pore-expanding agent and the deionized water is 5: 0.8: 10.

Wherein, the adding mol ratio of the components of the aluminum source, the phosphorus source, the silicon source, the deionized water, the nickel source, the template agent and the pore-expanding agent in the reaction kettle of the step S02 is 1: 1.5: 0.6: 70: 0.8: 5: 0.8; in step S03, the mixing mass ratio of the SAPO-11 carrier, the pseudo-boehmite and the sesbania powder is 80: 18: 4, the mass concentration of the acetic acid solution is 35%, and the adding amount of the acetic acid solution is 6% of the mass of the SAPO-11 carrier.

The parameters of the other steps in this embodiment are the same as those in embodiment 1, and are not described again.

Performance testing

The mass percent of nickel in the catalyst prepared in the embodiment is about 10.2% by adopting ICP (inductively coupled plasma) spectrometry, and then XRD (X-ray diffraction) is used for representing the state of the nickel in the catalyst, so that the nickel mainly exists in a nickel phosphide form; the mass fraction of the nickel phosphide in the catalyst is calculated by adopting the following calculation method:

w＝x×w1/(m1/m2)＝0.95×10.2％/(28×2/(28×2+15))＝12.3％；

wherein, w is the mass percentage of the nickel phosphide in the catalyst; x is a correction coefficient set to 0.95; m1 is the relative atomic mass of nickel in the nickel phosphide; m2 is the relative molecular mass of the nickel phosphide.

Example 4

This example is substantially the same as example 2, except that in step S04 of this example, the circulation of the phosphating solution was maintained at a flow rate of 0.5m/min after the introduction of the phosphating solution.

The parameters of the other steps in this embodiment are the same as those in embodiment 2, and are not described again.

Performance testing

The mass percent of nickel in the catalyst prepared in the embodiment is about 11.4% by adopting ICP (inductively coupled plasma) spectrometry, and then XRD (X-ray diffraction) is used for representing the state of the nickel in the catalyst, so that the nickel is mainly in the form of nickel phosphide; the mass fraction of the nickel phosphide in the catalyst is calculated by adopting the following calculation method:

w＝x×w1/(m1/m2)＝0.95×11.4％/(28×2/(28×2+15))＝13.7％；

wherein, w is the mass percentage of the nickel phosphide in the catalyst; x is a correction coefficient set to 0.95; m1 is the relative atomic mass of nickel in the nickel phosphide; m2 is the relative molecular mass of the nickel phosphide.

Example 5

This example is substantially the same as example 2, except that in step S04 of this example, the circulation of the phosphating solution was maintained at a flow rate of 1.0m/min after the introduction of the phosphating solution.

The parameters of the other steps in this embodiment are the same as those in embodiment 2, and are not described again.

Performance testing

The mass percent of nickel in the catalyst prepared in the embodiment is about 12.1% by adopting ICP (inductively coupled plasma) spectrometry, and then XRD (X-ray diffraction) is used for representing the state of the nickel in the catalyst, so that the nickel mainly exists in a nickel phosphide form; the mass fraction of the nickel phosphide in the catalyst is calculated by adopting the following calculation method:

w＝x×w1/(m1/m2)＝0.95×12.1％/(28×2/(28×2+15))＝14.6％；

wherein, w is the mass percentage of the nickel phosphide in the catalyst; x is a correction coefficient set to 0.95; m1 is the relative atomic mass of nickel in the nickel phosphide; m2 is the relative molecular mass of the nickel phosphide.

Example 6

This example is substantially the same as example 2, except that in step S04 of this example, the circulation of the phosphating solution was maintained at a flow rate of 1.5m/min after the introduction of the phosphating solution.

The parameters of the other steps in this embodiment are the same as those in embodiment 2, and are not described again.

Performance testing

The mass percent of nickel in the catalyst prepared in the embodiment is about 11.6% by adopting ICP (inductively coupled plasma) spectrometry, and then XRD (X-ray diffraction) is used for representing the state of the nickel in the catalyst, so that the nickel is mainly in the form of nickel phosphide; the mass fraction of the nickel phosphide in the catalyst is calculated by adopting the following calculation method:

w＝x×w1/(m1/m2)＝0.95×11.6％/(28×2/(28×2+15))＝14.0％；

wherein, w is the mass percentage of the nickel phosphide in the catalyst; x is a correction coefficient set to 0.95; m1 is the relative atomic mass of nickel in the nickel phosphide; m2 is the relative molecular mass of the nickel phosphide.

Based on the embodiments 1 to 6, it can be known that, in step S04, the catalyst precursor is immersed in the flowing phosphating solution to facilitate permeation and diffusion of the phosphating solution, so as to increase the yield of nickel phosphide, which is characterized in that the flowing phosphating solution generates a certain diffusion and permeation force, and the phenomenon that the diffusion of the phosphating solution is affected by blocking bubbles generated by the escaping air in the catalyst precursor is avoided.

Application testing

(1) The catalysts prepared in the examples 1 to 6 are filled in a reactor to prepare 6 application test groups;

(2) pumping fatty acid methyl ester into 6 groups of reactors of an application test group at a preset temperature of 270 +/-2 ℃ and a preset hydrogen pressure of 4.4-4.5 Mpa, and carrying out hydrodeoxygenation-isomerization reaction on the fatty acid methyl ester to obtain normal paraffin and isoparaffin with the same length as the fatty acid carbon chain in the fatty acid methyl ester.

Wherein the carbon chain length of fatty acid in the fatty acid methyl ester is 16-22, and the volume ratio of hydrogen to the fatty acid methyl ester is 700.

At a space velocity of 1.0h of the volume of the raw material^-1Under the conditions of (1), each application test group is subjected to hydrodeoxygenation-isomerization catalyst evaluation (evaluation mainly on isoparaffin catalysis), after the reaction is stable, sampling and analyzing are carried out, the raw material conversion rate and the paraffin yield are counted, and the results are as follows:

TABLE 1 statistics of conversion and yield of raw materials

According to the test results, the catalysts prepared in the embodiments of the present invention have excellent catalytic performance, and the mass ratio of nickel phosphide supported on the catalyst has positive correlation with the raw material deoxidation rate and isoparaffin yield when the nickel phosphide is applied.

The foregoing is directed to embodiments of the present invention, and equivalents, modifications, substitutions and variations such as will occur to those skilled in the art, which fall within the scope and spirit of the appended claims.