Preparation method of environmentally friendly plasticizer material and hydrogenation catalyst from diisononyl phthalate.

Abstract

This invention belongs to the field of catalysis technology, specifically relating to a method for preparing an environmentally friendly hydrogenation catalyst for plasticizer materials based on diisononyl phthalate. Using magnesium aluminum silicate as a substrate, a modified calcium aluminum composite support is prepared. Then, the active components Os and Zr are simultaneously loaded onto the support using a low-temperature, equal-volume impregnation method to obtain the finished catalyst. The diisononyl phthalate hydrogenation catalyst prepared using this invention maintains good selectivity, activity, and stability even under long-term operation in a continuous trickle-bed reactor with a low hydrogen-to-ester ratio. The active component Zr and the noble metal active component Os competitively adsorb onto the support to form a stable structure, resulting in low Os content and low loss rate, thus demonstrating good catalyst stability.

Description

Technical Field

[0001] This invention belongs to the field of catalysis technology, specifically relating to a method for preparing a catalyst based on the hydrogenation of diisononyl phthalate to cyclohexane 1,2-dicarboxylate. Background Technology

[0002] In recent years, with the increasing awareness of environmental protection and the growing demand for healthy living, low-toxicity phthalate plasticizers (such as DINP) used in food packaging and the pharmaceutical industry have been increasingly rejected, showing a trend of being replaced by non-toxic alternatives with strong comprehensive performance (such as DINCH). Furthermore, my country's plastics industry has developed rapidly, with the plasticizer industry growing at a rate of over 10% annually. The annual production capacity of phthalate plasticizers (such as DINP) has exceeded 3 million tons, resulting in overcapacity. One way to solve these two problems is to hydrogenate the excess DINP into non-toxic DINCH.

[0003] BASF in Germany used a Ru / Al2O3 catalyst prepared under patent US6284917B1 to achieve the industrialization of hydrogenation of diisononyl phthalate at 20 MPa. However, the reaction conditions are harsh and need to be carried out under ultra-high pressure, which places high demands on reactor materials and safety management during the production process.

[0004] US Patent US7361714B2 describes a supported catalyst of Ru, Pt, Rh, Co or Ni. When the mass fraction of Ru is 1%, the yield of DINCH can reach 99.5% at a temperature of 120°C and a pressure of 20 MPa for 2 hours. However, the reaction pressure is high and there is no data on long-term operation, so the stability of the catalyst is unknown.

[0005] Chinese patent CN115709064A describes an eggshell-type selective hydrogenation catalyst for the preparation of DINCH. Its active components consist of noble metals and lanthanides. In a fixed-bed microreactor, under conditions of 150°C, 4.0 MPa, and a hydrogen-to-ester ratio of 600:1, the feed conversion rate is 86-100%, and the product selectivity is 80-99.61%. However, the reaction pressure is low, but the hydrogen-to-ester ratio is too high, and the reaction volume is small (only 1 g). If the influence of internal diffusion cannot be eliminated, the scale-up effect cannot be predicted.

[0006] Chinese patent CN111036279A describes a Ru / HY zeolite-SiO2 catalyst. After 1.1g of catalyst was loaded into a 100ml batch reactor at 100℃ and 1~2MPa and reacted for 4h, the DINP conversion rate reached 99.9% and the DINCH yield reached 99.9%. Although the reaction pressure decreased significantly, the reaction volume was small and the reaction was carried out in a non-continuous state. The data was only tested after 4h of reaction, so the stability is unknown.

[0007] Currently, existing hydrogenation technologies for phthalates still suffer from problems such as harsh reaction conditions, small reaction scale, short reaction time, inability to achieve continuous processes, and excessively high hydrogen-ester ratios, which hinder the domestic industrialization of phthalate hydrogenation to cyclohexanedicarboxylate.

[0008] Therefore, those skilled in the art aim to prepare catalysts with excellent activity and stability that can adapt to low hydrogen-to-ester ratios in a continuous reaction process under relatively mild reaction conditions. However, under these conditions, since the reaction pressure is relatively low compared to traditional mature reaction processes abroad, the catalyst needs to possess good selectivity and stability to ensure a low hydrogen-to-ester ratio while continuously passing through the catalyst bed. This requires the development of catalysts with strong bonding between the active component and the support and suitable parameters such as porosity, thereby enhancing the contact and mass transfer between the gas and liquid phases on the catalyst surface. Ultimately, this achieves the goal of obtaining good product selectivity and feed conversion even under low pressure, low hydrogen-to-ester ratio, and long-term continuous passage through the catalyst bed. Summary of the Invention

[0009] The purpose of this invention is to provide a method for preparing an environmentally friendly hydrogenation catalyst for plasticizer materials based on diisononyl phthalate. This method solves the problems of poor catalyst activity, selectivity, and stability during long-term operation in a continuous trickle bed reactor under low pressure and hydrogen-to-ester ratio conditions.

[0010] The main features of this invention are:

[0011] 1) Magnesium aluminum silicate serves as both a dispersant and a structure modifier, playing an auxiliary role in the neutralization reaction of alkaline solution and aluminum nitrate solution in parallel flow, resulting in a primary modified sodium aluminum or potassium aluminum or sodium potassium aluminum suspension. This suspension is then mixed with calcium hydroxide and modified with dilute hydrochloric acid to form a secondary modified calcium sodium aluminum or calcium potassium aluminum or calcium sodium potassium aluminum support precursor. After filtration, drying, and calcination, a multidimensional layered support structure with crystal forms such as Na-Al-O-Ca, Ca-O-Al-K, Al-O-Na, Al-OO-Al, Al-OO-Ca, Ca-O-Al-KO-Mg, Ca-O-Al-Na-Mg-O-Si, and Ca-O-Al-K-Mg-O-Si is formed. Such a support has a high degree of binding with the active components Os and Zr and suitable pores, thereby improving the activity and stability of the catalyst.

[0012] 2) Using Os-Zr bimetal as the active component, the support is impregnated in a mixed salt solution of Os and Zr under low temperature conditions using an equal volume impregnation method, so that the bimetallic active components compete to be adsorbed onto the support. Subsequently, calcination is carried out to achieve a high degree of bonding between the bimetallic components and the support, so that the catalyst can maintain good DINCH hydrogenation selectivity even after long-term use.

[0013] This invention provides a method for preparing an environmentally friendly plasticizer material hydrogenation catalyst derived from diisononyl phthalate: The method is characterized by using a magnesium aluminum silicate dispersion as the base liquid, with an alkaline solution and an aluminum nitrate solution added concurrently for neutralization to obtain a primary modified sodium aluminum or potassium aluminum or sodium potassium aluminum suspension. This suspension is then mixed with calcium hydroxide and modified with dilute hydrochloric acid to form a secondary modified calcium sodium aluminum or calcium potassium aluminum or calcium sodium potassium aluminum support precursor. This precursor is then filtered, dried, and calcined to form a multidimensional layered support. At low temperature, the support is impregnated in a mixed salt solution of Os and Zr using an equal-volume impregnation method to obtain the catalyst precursor. Finally, the catalyst product is obtained through washing, drying, and calcination.

[0014] Furthermore, the preparation method of the catalyst of the present invention includes the following steps:

[0015] a. Prepare a magnesium aluminum silicate dispersion by mixing magnesium aluminum silicate and water at a mass ratio of 0.2~0.4:100;

[0016] b. Prepare a 0.2-0.4 mol / L aluminum nitrate solution rich in metallic aluminum ions; prepare a 1.25-2.5 mol / L alkaline precipitant.

[0017] c. Under constant temperature and stirring, add the two solutions obtained in step b to the dispersion obtained in step a in parallel flow for neutralization and precipitation, and control the final pH value to 7.2~8.0 to obtain a primary sodium aluminum or potassium aluminum or sodium potassium aluminum suspension.

[0018] d. Dissolve calcium hydroxide in water to prepare a 0.125~0.25mol / L (calculated as metallic calcium) suspension. Control the stirring speed at 150~350rpm. Slowly add the suspension obtained in step c, and simultaneously slowly add a dilute hydrochloric acid solution with a volume ratio of 1:10~1:15. Control the final pH value to 7.5 to obtain a secondary calcium sodium aluminum or calcium potassium aluminum or calcium sodium potassium aluminum suspension.

[0019] e. Filter the suspension obtained in step d, dry it for the first time, calcine it for the first time, and sieve it to obtain a 5-10 mesh carrier;

[0020] f. Prepare a mixed aqueous solution of 0.008~0.016 mol / L rich in active component osmium and 0.04~0.12 mol / L rich in active component zirconium, control the temperature at 10~20℃, and immerse the support obtained in step e in it for 1~2 h using the equal volume impregnation method to obtain the catalyst precursor; then immerse the impregnated catalyst precursor in 5%~8% (by mass) NaBH4 solution for 1~2 h, take it out, wash it with distilled water, dry it a second time, and calcine it a second time to obtain the finished catalyst.

[0021] Preferably, the aluminum nitrate solution mentioned in the above steps is a solution of aluminum nitrate nonahydrate dissolved in water, and the alkaline precipitant is a solution of one or both of sodium hydroxide and potassium hydroxide dissolved in water, and the Na:K molar ratio of the mixed sodium hydroxide and potassium hydroxide solution is 1:1.

[0022] The constant temperature mentioned in the above steps is achieved using an oil bath at a temperature of 50~70℃ and a stirring speed of 100~300rpm.

[0023] In the above steps, the aluminum nitrate solution is added at a rate of 15-30 ml / min during co-current flow, and the alkaline precipitant is added at a rate of 10-20 ml / min.

[0024] The mixed solution of active components osmium and zirconium mentioned in the above steps is a mixture of potassium osmium chloride and zirconium nitrate.

[0025] The molar ratio of Al:Ca in the carrier described in the above steps is 0.8~1.6:1.

[0026] The first drying temperature mentioned in the above steps is 120~160℃, and the first calcination temperature is 550~650℃.

[0027] In the above steps, the loading amounts of the active components osmium and zirconium are 0.06~0.12% and 0.15~0.45% of the catalyst weight, respectively.

[0028] The second drying temperature mentioned in the above steps is 110~130℃, the second calcination temperature is 350~450℃, and the calcination atmosphere is nitrogen.

[0029] The hydrogenation catalyst for diisononyl phthalate prepared by this invention maintains good selectivity, activity, and stability even under long-term operation in a continuous trickle bed reactor with a low hydrogen-to-ester ratio. The active component Zr and the noble metal active component Os compete for adsorption on the support to form a stable structure. The amount of noble metal Os used is small and the loss rate is low, resulting in good catalyst stability. Attached Figure Description

[0030] Figure 1 This is a photograph of the microstructure of the carrier in an embodiment of the present invention. Implementation

[0031] The method of the present invention will be described in detail below with reference to the embodiments and accompanying drawings. However, the embodiments are only for illustrating the invention and do not constitute a limitation on the scope of the present invention. Example 1

[0032] 1) Prepare a 1L magnesium aluminum silicate dispersion by mixing magnesium aluminum silicate and water at a mass ratio of 0.2:100; 2) Take 1L each of a 0.2mol / L aluminum nitrate solution rich in metallic aluminum ions and a 1.25mol / L sodium hydroxide solution; 3) Under a constant temperature oil bath at 50℃, control the stirring speed at 100rpm, and add the aluminum nitrate and sodium hydroxide solutions in parallel to the magnesium aluminum silicate dispersion for neutralization and precipitation. Control the addition rate of the aluminum nitrate solution at 30ml / min and the addition rate of the sodium hydroxide solution at 15ml / min. The final pH value is 7.2 to obtain a primary sodium aluminum or potassium aluminum or sodium potassium aluminum suspension; 4) Take 1L of a 0.25mol / L (calculated as metallic calcium) calcium hydroxide suspension, control the stirring speed at 350rpm, and slowly add the primary sodium aluminum suspension, while... 5) Slowly add a 1:10 volume ratio of dilute hydrochloric acid solution, controlling the final pH value to 7.5, to obtain a secondary calcium-sodium-aluminum suspension; 6) Filter the secondary calcium-sodium-aluminum suspension, dry at 160℃, calcine at 550℃, and sieve to obtain a 5-10 mesh support; 7) Prepare a 0.008 mol / L mixed aqueous solution rich in active component osmium and 0.12 mol / L rich in active component zirconium, control the temperature at 20℃, and immerse the support in it for 2 hours using the equal volume impregnation method to obtain a catalyst precursor; 8) Immerse the impregnated catalyst precursor in a 5% (by mass) NaBH4 solution for 1 hour, remove it, wash it once with distilled water, dry it at 110℃, and calcine it at 350℃ under a nitrogen atmosphere to obtain catalyst product I rich in 0.06% Os-0.45% Zr active components. Example 2

[0033] 1) Prepare a 1L magnesium aluminum silicate dispersion by mixing magnesium aluminum silicate and water at a mass ratio of 0.4:100; 2) Take 1L each of a 0.4mol / L aluminum nitrate solution rich in metallic aluminum ions and a 1.5mol / L potassium hydroxide solution; 3) Under a constant temperature oil bath at 70℃, with a stirring speed of 200rpm, add the aluminum nitrate and potassium hydroxide solutions concurrently to the magnesium aluminum silicate dispersion for neutralization and precipitation. Control the addition rate of the aluminum nitrate solution at 15ml / min and the addition rate of the potassium hydroxide solution at 20ml / min. The final pH value is 8.0 to obtain a primary potassium aluminum suspension; 4) Take 2L of a 0.125mol / L (calculated as metallic calcium) calcium hydroxide suspension, control the stirring speed at 250rpm, and slowly add the primary potassium aluminum suspension while simultaneously adding it dropwise. 5) Add a dilute hydrochloric acid solution with a volume ratio of 1:15, control the final pH value to 7.6, and prepare a secondary calcium-potassium-aluminum suspension; 6) Filter the secondary calcium-potassium-aluminum suspension, dry it at 160℃, calcine it at 650℃, and sieve it to obtain a 5-10 mesh support; 7) Prepare a mixed aqueous solution rich in active component osmium (0.008 mol / L) and active component zirconium (0.04 mol / L), control the temperature at 10℃, and immerse the support in it for 1 hour using the equal volume impregnation method to obtain a catalyst precursor; 8) Immerse the impregnated catalyst precursor in an 8% (by mass) NaBH4 solution for 1 hour, take it out, wash it once with distilled water, dry it at 110℃, and calcine it at 450℃ under a nitrogen atmosphere to obtain catalyst product II rich in active components of 0.06% Os-0.15% Zr. Example 3

[0034] 1) Prepare a 1L magnesium aluminum silicate dispersion by mixing magnesium aluminum silicate and water at a mass ratio of 0.3:100; 2) Take 1L each of a 0.4mol / L aluminum nitrate solution rich in metallic aluminum ions and a 1.25mol / L potassium hydroxide solution; 3) Under a constant temperature oil bath at 60℃, control the stirring speed at 200rpm, and add the aluminum nitrate and potassium hydroxide solutions concurrently to the magnesium aluminum silicate dispersion for neutralization and precipitation. Control the addition rate of the aluminum nitrate solution at 25ml / min and the addition rate of the potassium hydroxide solution at 15ml / min. The final pH value is 7.8 to obtain a primary potassium aluminum suspension; 4) Take 1.4L of a 0.179mol / L (calculated as metallic calcium) calcium hydroxide suspension, control the stirring speed at 350rpm, and slowly add the primary potassium aluminum suspension, while... 5) Slowly add a dilute hydrochloric acid solution with a volume ratio of 1:12, controlling the final pH value to 7.5, to obtain a secondary calcium-potassium-aluminum suspension; 6) Filter the secondary calcium-potassium-aluminum suspension, dry at 140℃, calcine at 600℃, and sieve to obtain a 5-10 mesh support; 7) Prepare a mixed aqueous solution rich in active components osmium (0.016 mol / L) and zirconium (0.04 mol / L), control the temperature at 15℃, and immerse the support in the solution for 2 hours using an equal-volume impregnation method to obtain a catalyst precursor; 8) Immerse the impregnated catalyst precursor in a 6% (by mass) NaBH4 solution for 1 hour, remove it, wash it once with distilled water, dry it at 130℃, and calcine it at 400℃ under a nitrogen atmosphere to obtain catalyst product III rich in active components 0.12% Os-0.15% Zr. Example 4

[0035] 1) Prepare a 1L magnesium aluminum silicate dispersion by mixing magnesium aluminum silicate and water at a mass ratio of 0.25:100; 2) Take 1L each of a 0.3mol / L aluminum nitrate solution rich in metallic aluminum ions and a 2.0mol / L mixed solution of sodium hydroxide and potassium hydroxide; 3) Under a constant temperature oil bath at 70℃, control the stirring speed at 300rpm, and add the aluminum nitrate, sodium hydroxide, and potassium hydroxide mixed solution in parallel streams to the magnesium aluminum silicate dispersion for neutralization and precipitation. Control the addition rate of the aluminum nitrate solution at 25ml / min and the addition rate of the sodium hydroxide and potassium hydroxide mixed solution at 10ml / min. The final pH value is 7.4 to obtain a primary sodium potassium aluminum suspension; 4) Take 1.25L of a 0.2mol / L (calculated as metallic calcium) calcium hydroxide suspension, control the stirring speed at 200rpm, and add the primary sodium potassium aluminum suspension to the magnesium aluminum silicate dispersion. 5) The suspension was slowly added, and simultaneously a dilute hydrochloric acid solution with a volume ratio of 1:13 was slowly added dropwise, controlling the final pH value to 7.5, to obtain a secondary calcium, sodium, potassium, and aluminum suspension; 6) The calcium, sodium, potassium, and aluminum suspension was filtered, dried at 160℃, calcined at 550℃, and sieved to obtain a 5-10 mesh support; 7) A mixed aqueous solution rich in active component osmium (0.012 mol / L) and active component zirconium (0.08 mol / L) was prepared, and the temperature was controlled at 15℃. The support was immersed in the solution for 1.5 h using an equal volume impregnation method to obtain a catalyst precursor; 8) The impregnated catalyst precursor was immersed in a 7% (by mass) NaBH4 solution for 1 h, then washed once with distilled water, dried at 130℃, and calcined at 450℃ under a nitrogen atmosphere to obtain catalyst product IV rich in active components of 0.09% Os-0.30% Zr. Example 5

[0036] 1) Prepare a 1L magnesium aluminum silicate dispersion by mixing magnesium aluminum silicate and water at a mass ratio of 0.2:100; 2) Take 1L each of a 0.4mol / L aluminum nitrate solution rich in metallic aluminum ions and a 2.5mol / L sodium hydroxide solution; 3) Under a constant temperature oil bath at 50℃, control the stirring speed at 300rpm, and add the aluminum nitrate and sodium hydroxide solutions in parallel streams to the magnesium aluminum silicate dispersion for neutralization and precipitation. Control the addition rate of the aluminum nitrate solution at 15ml / min and the addition rate of the sodium hydroxide solution at 10ml / min. The final pH value is 7.2 to obtain a primary sodium aluminum suspension; 4) Take 1L of a 0.25mol / L (calculated as metallic calcium) calcium hydroxide suspension, control the stirring speed at 350rpm, and slowly add the primary sodium aluminum suspension while simultaneously adding dropwise a volume ratio of 1: 5) Prepare a secondary calcium-sodium-aluminum suspension by dissolving a 10% dilute hydrochloric acid solution and controlling the final pH value to 7.5; 6) Filter the secondary calcium-sodium-aluminum or calcium-potassium-aluminum or calcium-sodium-potassium-aluminum suspension, dry it at 150℃, calcine it at 600℃, and sieve it to obtain a 5~10 mesh support; 7) Prepare a mixed aqueous solution rich in active component osmium and 0.08 mol / L rich in active component zirconium, control the temperature at 15℃, and immerse the support in it for 1.5h using the equal volume impregnation method to obtain the catalyst precursor; 8) Immerse the impregnated catalyst precursor in a 5% (by mass) NaBH4 solution for 1.5h, take it out, wash it once with distilled water, dry it at 120℃, and calcine it at 450℃ under nitrogen atmosphere to obtain the catalyst product V rich in active components of 0.075% Os-0.30% Zr. Example 6

[0037] 1) Prepare a 1L magnesium aluminum silicate dispersion by mixing magnesium aluminum silicate and water at a mass ratio of 0.35:100; 2) Take 1L each of a 0.25mol / L aluminum nitrate solution rich in metallic aluminum ions and a 1.75mol / L mixed solution of sodium hydroxide and potassium hydroxide; 3) Under a constant temperature oil bath at 60℃, with a stirring speed of 150rpm, add the aluminum nitrate, sodium hydroxide, and potassium hydroxide mixed solution in parallel streams to the magnesium aluminum silicate dispersion for neutralization and precipitation. Control the addition rate of the aluminum nitrate solution at 20ml / min and the addition rate of the sodium hydroxide and potassium hydroxide mixed solution at 20ml / min. The final pH value is 7.2 to obtain a primary sodium potassium aluminum suspension; 4) Take 1L of 0.25mol / L (calculated as metallic calcium) calcium hydroxide suspension, control the stirring speed at 250rpm, and add the primary sodium potassium aluminum suspension... 5) The suspension was slowly added, and simultaneously a dilute hydrochloric acid solution with a volume ratio of 1:10 was slowly added dropwise, controlling the final pH value to 7.5, to obtain a secondary calcium, sodium, potassium, and aluminum suspension; 6) The secondary calcium, sodium, potassium, and aluminum suspension was filtered, dried at 130℃, calcined at 600℃, and sieved to obtain a 5-10 mesh support; 7) A mixed aqueous solution rich in active components osmium (0.016 mol / L) and zirconium (0.12 mol / L) was prepared, and the temperature was controlled at 15℃. The support was immersed in the solution for 2 hours using an equal volume impregnation method to obtain a catalyst precursor; 8) The impregnated catalyst precursor was immersed in a 5% (by mass) NaBH4 solution for 2 hours, then washed once with distilled water, dried at 130℃, and calcined at 350℃ under a nitrogen atmosphere to obtain catalyst product VI rich in active components 0.12% Os-0.45% Zr. Example 7

[0038] 1) Prepare a 1L magnesium aluminum silicate dispersion by mixing magnesium aluminum silicate and water at a mass ratio of 0.2:100; 2) Take 1L each of a 0.35mol / L aluminum nitrate solution rich in metallic aluminum ions and a 2.0mol / L potassium hydroxide solution; 3) Under a constant temperature oil bath at 50℃, control the stirring speed at 100rpm, and add the aluminum nitrate and potassium hydroxide solutions in parallel streams to the magnesium aluminum silicate dispersion for neutralization and precipitation. Control the addition rate of the aluminum nitrate solution at 25ml / min and the addition rate of the potassium hydroxide solution at 10ml / min. The final pH value is 7.6 to obtain a primary potassium aluminum suspension; 4) Take 1L of a 0.25mol / L (calculated as metallic calcium) calcium hydroxide suspension, control the stirring speed at 150rpm, and slowly add the primary potassium aluminum suspension while simultaneously adding it dropwise. 5) Add a dilute hydrochloric acid solution with a volume ratio of 1:10, control the final pH value to 7.5, and obtain a secondary calcium-potassium-aluminum suspension; 6) Filter the secondary calcium-potassium-aluminum suspension, dry it at 120℃, calcine it at 580℃, and sieve it to obtain a 5-10 mesh support; 7) Prepare a mixed aqueous solution rich in active component osmium (0.008 mol / L) and active component zirconium (0.04 mol / L), control the temperature at 10℃, and immerse the support in it for 1 hour using the equal volume impregnation method to obtain a catalyst precursor; 8) Immerse the impregnated catalyst precursor in a 5% (by mass) NaBH4 solution for 1 hour, take it out, wash it once with distilled water, dry it at 110℃, and calcine it at 450℃ under a nitrogen atmosphere to obtain the catalyst product VII rich in active components of 0.06% Os-0.15% Zr. Example 8

[0039] 1) Prepare a 1L magnesium aluminum silicate dispersion by mixing magnesium aluminum silicate and water at a mass ratio of 0.3:100; 2) Take 1L each of a 0.2mol / L aluminum nitrate solution rich in metallic aluminum ions and a 2.25mol / L sodium hydroxide solution; 3) Under a constant temperature oil bath at 50℃, control the stirring speed at 200rpm, and add the aluminum nitrate and sodium hydroxide solutions in parallel to the magnesium aluminum silicate dispersion for neutralization and precipitation. Control the addition rate of the aluminum nitrate solution at 25ml / min and the addition rate of the sodium hydroxide solution at 20ml / min. The final pH value is 8.0 to obtain a primary sodium aluminum suspension; 4) Take 1L of 0.25mol / L (calculated as metallic calcium) calcium hydroxide suspension, control the stirring speed at 350rpm, and slowly add the primary sodium aluminum suspension while simultaneously adding water dropwise. 5) Prepare a secondary calcium-sodium-aluminum suspension by mixing a 1:10 volume ratio of dilute hydrochloric acid solution and controlling the final pH value to 7.5; 6) Filter the secondary calcium-sodium-aluminum suspension, dry it at 120℃, calcine it at 550℃, and sieve it to obtain a 5-10 mesh support; 7) Prepare a mixed aqueous solution rich in active components osmium and zirconium (0.014 mol / L), control the temperature at 10℃, and immerse the support in it for 2 hours using the equal volume impregnation method to obtain a catalyst precursor; 8) Immerse the impregnated catalyst precursor in a 5% (by mass) NaBH4 solution for 1 hour, wash it once with distilled water, dry it at 130℃, and calcine it at 400℃ under a nitrogen atmosphere to obtain the catalyst product VIII rich in active components 0.105% Os-0.15% Zr. Example 9

[0040] 1) Prepare a 1L magnesium aluminum silicate dispersion by mixing magnesium aluminum silicate and water at a mass ratio of 0.25:100; 2) Take 1L each of a 0.2mol / L aluminum nitrate solution rich in metallic aluminum ions and a 2.5mol / L mixed solution of sodium hydroxide and potassium hydroxide; 3) Under a constant temperature oil bath at 60℃, control the stirring speed at 200rpm, and add the mixed solution of aluminum nitrate, sodium hydroxide, and potassium hydroxide in parallel stream to the magnesium aluminum silicate dispersion for neutralization and precipitation. Control the addition rate of aluminum nitrate solution at 25ml / min and the addition rate of the mixed solution of sodium hydroxide and potassium hydroxide at 15ml / min. The final pH value is 7.8 to obtain a primary sodium potassium aluminum suspension; 4) Take 1L of 0.25mol / L (calculated as metallic calcium) calcium hydroxide suspension, control the stirring speed at 250rpm, and add the primary sodium potassium aluminum suspension... 5) The liquid was slowly added, and a dilute hydrochloric acid solution with a volume ratio of 1:10 was slowly added dropwise, controlling the final pH value to 7.5, to obtain a secondary calcium, sodium, potassium, and aluminum suspension; 6) The secondary calcium, sodium, potassium, and aluminum suspension was filtered, dried at 140℃, calcined at 600℃, and sieved to obtain a 5-10 mesh support; 7) A mixed aqueous solution rich in active components osmium and zirconium (0.008 mol / L) was prepared, and the temperature was controlled at 15℃. The support was immersed in the solution for 2 hours using an equal volume impregnation method to obtain a catalyst precursor; 8) The impregnated catalyst precursor was immersed in a 5% (by mass) NaBH4 solution for 2 hours, then washed once with distilled water, dried at 130℃, and calcined at 450℃ under a nitrogen atmosphere to obtain the catalyst product IX rich in active components 0.06% Os-0.30% Zr.

[0041] Comparative Example 1

[0042] 1) Prepare a 0.018 mol / L solution rich in the active component ruthenium; 2) Mix 30 g γ-Al2O3, 60 g calcium hydroxide, and 10 g potassium hydroxide with water until homogeneous, heat-treat at 500℃ for 2 h, and granulate to obtain a 5-10 mesh calcium-potassium-aluminum support. Then, impregnate an equal volume of the support in the above Ru salt solution for 2 h; 3) Take out the above primary catalyst precursor, dry at 130℃ for 2 h, and calcine at 450℃ for 2 h; 4) Prepare a 0.08 mol / L solution rich in the active component zirconium, impregnate the above secondary catalyst precursor again in the solution, and then dry at 130℃ for 2 h and calcine at 550℃ for 1 h to finally obtain catalyst product A rich in 0.09% Ru-0.30% Zr active components.

[0043] Comparative Example 2

[0044] 1) Prepare a 0.008 mol / L solution rich in the active component osmium; 2) Mix 30 g γ-Al2O3, 60 g calcium hydroxide, and 10 g potassium hydroxide with water until homogeneous, heat-treat at 500℃ for 2 h, and granulate to obtain a 5-10 mesh calcium potassium aluminum support. Then, impregnate an equal volume of the support in the above osmium salt solution for 2 h; 3) Take out the above primary catalyst precursor, dry at 130℃ for 2 h, and calcine at 450℃ for 2 h; 4) Prepare a 0.08 mol / L solution rich in the active component zirconium, impregnate the above secondary catalyst precursor again in the solution, and then dry at 130℃ for 2 h and calcine at 550℃ for 1 h to finally obtain catalyst product B rich in 0.06% Os-0.30% Zr active components.

[0045] Comparative Example 3

[0046] 1) Prepare a 0.008 mol / L solution rich in the active component osmium; 2) Mix 30 g γ-Al2O3, 50 g calcium hydroxide, 10 g sodium hydroxide, and 10 g potassium hydroxide with water until homogeneous, then heat-treat at 500℃ for 2 h and granulate to obtain a 5-10 mesh calcium-sodium-potassium-aluminum support. Then, impregnate an equal volume of the support in the above-mentioned mixed salt solution of osmium and zirconium for 2 h; 3) Immerse the impregnated catalyst precursor in a 5% (by mass) NaBH4 solution for 2 h, then remove and wash once with distilled water, dry at 130℃ for 2 h, and calcine at 450℃ for 2 h to finally obtain the catalyst product C rich in 0.06% Os active component.

[0047] Comparative Example 4

[0048] 1) Prepare 1 L each of a 0.3 mol / L aluminum nitrate solution rich in metallic aluminum ions and a 2.5 mol / L mixed solution of sodium hydroxide and potassium hydroxide; 2) In a constant temperature oil bath at 60℃, with a stirring speed of 200 rpm, add the mixed solution of sodium hydroxide and potassium hydroxide to the aluminum nitrate solution to neutralize and precipitate, thus obtaining a primary sodium-potassium-aluminum suspension; 3) Take 1 L of a 0.25 mol / L (calculated as metallic calcium) calcium hydroxide suspension, control the stirring speed at 250 rpm, and slowly add the primary sodium-potassium-aluminum suspension to obtain a secondary calcium-sodium suspension. 4) The secondary calcium, sodium, potassium and aluminum suspension was filtered, dried at 140℃, calcined at 600℃, and sieved to obtain a 5-10 mesh support; 5) A mixed aqueous solution rich in active components ruthenium (0.009 mol / L) and zirconium (0.04 mol / L) was prepared, and the support was immersed in it for 2 hours using the equal volume impregnation method to obtain the catalyst precursor; 6) The precursor was washed once with distilled water, dried at 130℃, and calcined at 450℃ to obtain the catalyst product D rich in active components 0.045% Os-0.15% Zr.

[0049] Comparative Example 5

[0050] 1) A silica-alumina composite carrier was obtained by uniformly mixing 100g alumina, 30g silica, and 5g cellulose, pressing into tablets, drying at 130℃ for 3 hours, and calcining at 550℃ for 4 hours; 2) A 0.008mol / L solution rich in the active component Ru was prepared. 3+ 3) The silicon-aluminum composite support was immersed in the solution for 2 hours; 4) After being removed, it was dried at 120°C for 2 hours and calcined at 400°C for 2 hours to obtain the catalyst product E rich in 0.04% active component Ru.

[0051] Comparative Example 6

[0052] 1) Mix 102g of alumina powder and 5g of cellulose evenly, extrude, dry at 130℃ for 3h, and calcine at 550℃ for 4h to obtain an Al2O3 support; 2) Prepare a 1mol / L salt solution rich in the active component cerium; 3) Impregnate the support with an equal volume for 2h, remove it, dry at 120℃ for 5h, and calcine at 300℃ for 2h to obtain a primary catalyst precursor; 4) Prepare a 0.18mol / L solution rich in the active component ruthenium, impregnate the primary catalyst precursor with an equal volume for 2h, remove it, dry at 120℃ for 5h, and calcine at 350℃ for 2h to obtain the catalyst product F rich in the active components 0.9%Ru-6.3%Ce.

[0053] Catalyst performance evaluation

[0054] Catalysts I-IX and comparative examples A-F were respectively packed into a continuous trickle bed reactor and reduced at 220℃ and 0.5 MPa under a hydrogen atmosphere for 1 h; the reaction temperature was 150℃, the hydrogen pressure was 3.0 MPa, and the liquid hourly space velocity was 0.6 h⁻¹. -1 The H2 / ester molar ratio was 50, and samples were taken for analysis at reaction times of 100 h and 500 h.

[0055] The evaluation results are shown in the table below.

[0056] .

[0057] The reaction data in the table show that catalysts I to IX prepared by this method exhibit good performance at a reaction temperature of 150℃, a reaction pressure of 3.0 MPa, and a liquid hourly space velocity of 0.6 h⁻¹. -1 Under the condition of an H2 / ester molar ratio of 50, both catalysts exhibited good DINP conversion and DINCH selectivity after 100 h and 500 h, demonstrating good stability. In contrast, while comparative examples A-F showed good conversion and selectivity in the initial stages of the reaction, their conversion and selectivity decreased to varying degrees after 500 h, indicating poor stability. Therefore, physicochemical analyses were performed on catalysts I-IX and comparative examples A-F after use. The results showed that the catalysts prepared by the method of this invention did not lose the noble metal Os and had a stable support structure (the support structure can be found in the appendix). Figure 1In contrast, in comparative examples A to F, precious metals were lost to varying degrees and the carrier channels were severely blocked.

Claims

1. A method for preparing a hydrogenation catalyst for an environmentally friendly plasticizer material derived from diisononyl phthalate, characterized by using... Magnesium aluminum silicate dispersion is used as the base liquid. Alkali solution and aluminum nitrate solution are added in parallel to neutralize the solution, resulting in a primary modified sodium aluminum or potassium aluminum or sodium potassium aluminum suspension. This suspension is then mixed with calcium hydroxide and modified with dilute hydrochloric acid to form a secondary modified calcium sodium aluminum or calcium potassium aluminum or calcium sodium potassium aluminum support precursor. After filtration, drying and calcination, a multi-dimensional layered support is formed. The support is impregnated in a mixed salt solution of Os and Zr at low temperature using an equal volume impregnation method to obtain the catalyst precursor. Finally, the catalyst product is obtained by washing, drying and calcination.

2. The preparation method according to claim 1, characterized in that... Includes the following steps: a. Prepare a magnesium aluminum silicate dispersion by mixing magnesium aluminum silicate and water at a mass ratio of 0.2~0.4:100; b. Prepare a 0.2-0.4 mol / L aluminum nitrate solution rich in metallic aluminum ions; prepare a 1.25-2.5 mol / L alkaline precipitant. c. Under constant temperature and stirring, add the two solutions obtained in step b to the dispersion obtained in step a in parallel flow for neutralization and precipitation, and control the final pH value to 7.2~8.0 to obtain a primary sodium aluminum or potassium aluminum or sodium potassium aluminum suspension. d. Dissolve calcium hydroxide in water to prepare a suspension of 0.125~0.25 mol / L based on metallic calcium. Control the stirring speed at 150~350 rpm. Slowly add the suspension obtained in step c, and simultaneously slowly add a dilute hydrochloric acid solution with a volume ratio of 1:10~1:

15. Control the final pH value to 7.5 to obtain a secondary calcium-sodium-aluminum or calcium-potassium-aluminum or calcium-sodium-potassium-aluminum suspension. e. Filter the suspension obtained in step d, dry it for the first time, calcine it for the first time, and sieve it to obtain a 5-10 mesh carrier; f. Prepare a mixed aqueous solution of 0.008~0.016 mol / L rich in active component osmium and 0.04~0.12 mol / L rich in active component zirconium, control the temperature at 10~20℃, and immerse the support obtained in step e in it for 1~2 h using the equal volume impregnation method to obtain the catalyst precursor; then immerse the impregnated catalyst precursor in a 5%~8% NaBH4 solution for 1~2 h, take it out, wash it with distilled water, dry it a second time, and calcine it a second time to obtain the finished catalyst.

3. The preparation method according to claim 2, characterized in that... The aluminum nitrate solution is a solution made by dissolving aluminum nitrate nonahydrate in water; the alkaline precipitant is a solution made by dissolving one or both of sodium hydroxide or potassium hydroxide in water, and the Na:K molar ratio of the mixed sodium hydroxide and potassium hydroxide solution is 1:

1.

4. The preparation method according to claim 2, characterized in that... The constant temperature is achieved using an oil bath at a temperature of 50~70℃, with a stirring speed of 100~300rpm.

5. The preparation method according to claim 2, characterized in that... When the flow is parallel, the aluminum nitrate solution is added at a rate of 15-30 ml / min, and the alkaline precipitant is added at a rate of 10-20 ml / min.

6. The preparation method according to claim 2, characterized in that... The active components, osmium and zirconium, are a mixture of potassium osmium chloride and zirconium nitrate.

7. The preparation method according to claim 2, characterized in that... The molar ratio of Al:Ca in the carrier is 0.8~1.6:

1.

8. The preparation method according to claim 2, characterized in that... The first drying temperature is 120~160℃, and the first roasting temperature is 550~650℃.

9. The preparation method according to claim 2, characterized in that... The loadings of the active components osmium and zirconium are 0.06~0.12% and 0.15~0.45% of the catalyst weight, respectively.

10. The preparation method according to claim 2, characterized in that... The second drying temperature is 110~130℃, the second calcination temperature is 350~450℃, and the calcination atmosphere is nitrogen.

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