阅读说明：本技术 邻苯二甲酸酯加氢催化剂的制备方法 (Preparation method of phthalate hydrogenation catalyst ) 是由 张�杰 殷玉圣 于杨 黄先亮 徐本刚 王金利 蔡进 吴学其 朱艳芳 于 2018-06-25 设计创作，主要内容包括：本发明属于催化技术领域,具体涉及一种邻苯二甲酸酯加氢用催化剂的制备方法。采用特殊方法制备纳米级硅铝前驱体,通过锆、钾、铜等多金属组分的协同作用,得到具有良好比表面积、孔容、孔径的载体；再将活性组分Rh负载于载体上,用KBH<Sub>4</Sub>溶液进行处理后得到催化剂成品。采用本发明制备的邻苯二甲酸酯加氢用催化剂,在滴流床反应器中使用,无需在氢气下还原,在较低反应压力下,即表现出良好的活性、选择性,同时,贵金属流失率低,稳定性好。(The invention belongs to the technical field of catalysis, and particularly relates to a preparation method of a catalyst for hydrogenation of phthalate. Preparing a nano-scale silicon-aluminum precursor by a special method, and obtaining a carrier with good specific surface area, pore volume and pore diameter through the synergistic effect of multiple metal components such as zirconium, potassium, copper and the like; then loading active component Rh on the carrier, using KBH 4 Solution feedingAnd treating to obtain a catalyst finished product. The catalyst for hydrogenation of phthalate prepared by the invention is used in a trickle bed reactor, does not need to be reduced under hydrogen, shows good activity and selectivity under lower reaction pressure, and simultaneously has low loss rate of noble metal and good stability.)

1. A preparation method of a phthalate hydrogenation catalyst is characterized in that the catalyst is obtained by the following steps:

(1) preparation of the carrier:

dissolving one or two of pseudo-boehmite or aluminum hydroxide in water to prepare suspension;

adding 2 ~ 10% dilute nitric acid into the suspension liquid in the step a under stirring to obtain aluminum sol;

fully mixing the silicate solution and the aluminum sol, and modulating the pH of the mixture by using alkali liquor to prepare silicon-aluminum sol;

drying, roasting and crushing the material obtained in the step c to obtain a silicon-aluminum nano-scale composite material;

adding the material obtained in the step d into a binder, and simultaneously adding an X oxide to perform mixing, tabletting and molding to obtain a carrier precursor, wherein the X oxide is one or more of oxides of zirconium, copper, zinc, manganese, cerium, magnesium and potassium;

roasting the carrier precursor to obtain a carrier;

(2) preparation of active ingredients:

dissolving Rh salt in water, adding a KOH solution to adjust the pH value, and obtaining an impregnation liquid rich in active components;

(3) preparation of the catalyst:

h. soaking the carrier obtained in the step f in the soaking solution prepared in the step g for 0.5 ~ 1h in the same volume;

i. stirring KBH at room temperature₄And (5) adding the aqueous solution into the material obtained in the step h, reducing for 1 ~ 2h, taking out the impregnated catalyst precursor, washing with water, and drying to obtain the catalyst.

2. The method according to claim 1, wherein the molar ratio of Si to Al to X in the carrier is 1:1 ~ 3:0.05 ~ 0.2.2.

3. The process according to claim 1, wherein the loading of active component Rh is 0.1% ~ 2% by weight of the catalyst, and the catalyst does not need to be reduced in hydrogen before use.

4. The preparation method according to claim 1, wherein the stirring speed in the preparation step b is 80 ~ 200r/min, the temperature is controlled at 40 ~ 60 ℃ and the treatment time is 0.5h ~ 1.5.5 h, the stirring speed in the step c is 150 ~ 280r/min, the temperature is controlled at 60 ~ 80 ℃ and the treatment time is 1h ~ 2h, and the pH value is 7 ~ 9.

5. The method according to claim 1, wherein the silicate in step c is one or more selected from sodium silicate, magnesium silicate, aluminum silicate, iron silicate, calcium silicate and potassium silicate; the alkali solution is one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, potassium hydroxide and potassium bicarbonate.

6. The method of claim 1, wherein the firing temperature in step d is 900 ~ 1100 ℃ and the firing time is 3 ~ 5 hours.

7. The method of claim 1, wherein the carrier sheet is formed to have a dimension Φ 3 x 3mm in the step e.

8. The method of claim 1, wherein the calcination temperature in step f is controlled at 300 ~ 500 ℃ for 1 ~ 2 h.

9. The process of claim 1, wherein the KOH solution in preparation step g has a concentration of 0.05 ~ 0.2.2 mol/L and a pH of 7 ~ 7.5.5.

10. The method of claim 1, wherein the temperature in step h is controlled to 50 ~ 70 ℃.

Technical Field

The invention belongs to the technical field of catalysis, and particularly relates to a preparation method of a phthalate hydrogenation catalyst.

Background

The plasticizer is a widely used plastic additive, and the phthalate plasticizer is dominant in products in the industry. Since the 90 s in the 20 th century, researches show that phthalate causes endocrine disorders in human bodies, and liver cancer can be caused by a large amount of phthalate taken for a long time. At present, the use of phthalate plasticizers in food packaging and children toys is regulated by various legislations in the regions and countries of the European Union, the United states, Japan and the like. The development and research of novel, nontoxic and environment-friendly plasticizers become the focus of attention. The direct benzene ring hydrogenation of phthalate ester to generate cyclohexane 1, 2-diformate is a hotspot of current research, and is expected to replace phthalate ester plasticizers in the future.

The patent US475064 describes that in the temperature range of 90 ℃ ~ ℃ the synthesis of cyclohexanedicarboxylic acid by using 5% by mass of Rh/C catalyst, the synthesis of cyclohexanedicarboxylic acid by using 5% by mass of Rh/C catalyst is high, the active component Rh content of noble metal is high, and the stability of the catalyst is not reported.Chinese patent CN106984310A discloses a preparation method of phthalate hydrogenation catalyst, wherein noble metal Ru is selected as the active component, a carrier is one of zirconia, magnesia, silica or alumina, and the like, an intermittent hydrogenation process is adopted, the catalyst needs to be reduced for 3 ~ h under the hydrogen atmosphere at 100 ~ ℃, the product yield is 99.49%, the reduction time is long, and the loss rate and the stability of noble metal are not known yet.

At present, in the aspect of phthalate hydrogenation, a hydrogenation catalyst with high activity, high selectivity and good stability is prepared under relatively mild reaction conditions, which is an important subject to be solved by researchers at present.

Disclosure of Invention

The purpose of the invention is as follows: provides a preparation method of a phthalate hydrogenation catalyst. The problems of low conversion rate, low selectivity, poor stability and the like of the catalyst under the condition of low reaction pressure are solved; the problem that the catalyst needs to be reduced in a hydrogen atmosphere for a long time before hydroconversion is solved, and the production period is shortened.

The invention has the main characteristics that:

1) preparing a nano-scale silicon-aluminum precursor by a special method, and obtaining a carrier with good specific surface area, pore volume and pore diameter by the synergistic effect of multi-metal components such as zirconium, copper and the like;

2) the loading rate of the precious metal Rh is low, the metal loss rate of the catalyst is low after the catalyst is used for a long time, and the stability is good;

3) before the catalyst is used, reduction and activation are not needed, the use cost of hydrogen in the reaction is reduced, and the production period of the plasticizer is shortened.

The main technical scheme of the invention is as follows: the preparation method of the phthalate ester hydrogenation catalyst is characterized in that the catalyst is obtained by the following steps:

(1) preparation of the carrier:

a. dissolving one or two of pseudo-boehmite or aluminum hydroxide in water to prepare suspension;

b. adding 2 ~ 10% dilute nitric acid into the suspension liquid in the step a under stirring to obtain aluminum sol;

c. fully mixing the silicate solution and the aluminum sol, and modulating the pH of the mixture by using alkali liquor to prepare silicon-aluminum sol;

d. drying, roasting and crushing the material obtained in the step c to obtain a silicon-aluminum nano-scale composite material;

adding the material obtained in the step d into a binder, and simultaneously adding an X oxide to perform mixing, tabletting and molding to obtain a carrier precursor, wherein the X oxide is one or more of oxides of zirconium, copper, zinc, manganese, cerium, magnesium and potassium;

e. roasting the carrier precursor to obtain a carrier;

(2) preparation of active ingredients:

f. dissolving Rh salt in water, adding a KOH solution to adjust the pH value, and obtaining an impregnation liquid rich in active components;

(3) preparation of the catalyst:

h. soaking the carrier obtained in the step f in the soaking solution prepared in the step g for 0.5 ~ 1h in the same volume;

i. stirring KBH at room temperature₄And (5) adding the aqueous solution into the material obtained in the step h, reducing for 1 ~ 2h, taking out the impregnated catalyst precursor, washing with water, and drying to obtain the catalyst.

Typically, the molar ratio of Si to Al to X in the support is 1:1 ~ 3:0.05 ~ 0.2.2.

The loading amount of the active component Rh is 0.1 percent ~ 2 percent of the weight of the catalyst, and the catalyst does not need to be reduced in hydrogen before use.

The stirring speed in the preparation step b is 80 ~ 200r/min, the temperature is controlled at 40 ~ 60 ℃ and the treatment time is 0.5h ~ 1.5h, the stirring speed in the step c is 150 ~ 280r/min, the temperature is controlled at 60 ~ 80 ℃ and the treatment time is 1h ~ 2h, and the pH value is 7 ~ 9.

The silicate in the preparation step c is one or more of sodium silicate, magnesium silicate, aluminum silicate, ferric silicate, calcium silicate and potassium silicate; the alkali solution is one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, potassium hydroxide and potassium bicarbonate.

The roasting temperature in the preparation step d is 900 ~ 1100 ℃, and the roasting time is 3 ~ 5 h.

And in the preparation step e, the forming size of the carrier pressing sheet is phi 3 multiplied by 3 mm.

In the preparation step f, the roasting temperature is controlled at 300 ~ 500 ℃ for 1 ~ 2 h.

The concentration of the KOH solution in the preparation step g is 0.05 ~ 0.2mol/L, and the pH value is 7 ~ 7.5.5.

The temperature in the preparation step h was controlled at 50 ~ 70 ℃.

A typical laboratory preparation procedure of the present invention is as follows:

1) dissolving 10 4630 g of pseudoboehmite or one or two of aluminum hydroxide in water to prepare a suspension, 2) controlling the stirring speed to be 80 ~ r/min and the temperature to be 40 ~ ℃ and adding 2 ~% of dilute nitric acid into the suspension to be treated for 0.5 ~.5 h, 3) controlling the stirring speed to be 60 3680 ℃ and the stirring speed to be 150 ~ r/min, then adding 10 4630 g of one or more of sodium silicate, magnesium silicate, aluminum silicate, ferric silicate, calcium silicate and potassium silicate into the suspension to be treated for 1 ~ h, adjusting the pH value of the material to be 7 ~ by using one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, potassium hydroxide and potassium bicarbonate, 4) taking out the material to be dried at 120 ℃, roasting at 900 ~ ℃ to 1100 ℃ for 3 ~ h, crushing, adding a binder, fully mixing 5g of one or more of oxides of zirconium, copper, zinc, manganese, cerium, magnesium and potassium at phi of 3 x 3h, tabletting, and forming the mixture into tablets at ~ mm, and forming the carrier to be 500 ml of 465 g of₃•3H₂Dissolving O in water to obtain solution with concentration of 0.001g/ml ~ 0.02.02 g/ml (calculated by Rh metal), adding KOH solution of 0.05 ~ 0.2.2 mol/L to adjust pH to 7 ~ 7.5.5 to obtain active component immersion liquid, 6) immersing the shaped carrier in the immersion liquid at 50 ~ 70 deg.C for 0.5 ~ 1h, 7) cooling to room temperature, and stirring to obtain KBH₄Adding the aqueous solution into a carrier for reduction for 1 ~ 2h, and 8) taking out the reduced catalyst precursor, washing with water and drying to obtain a finished catalyst product with the Rh mass content of 0.1 percent ~ 2 percent.

The catalyst for hydrogenation of phthalate prepared by the invention has good activity and selectivity under lower reaction pressure without reduction under hydrogen, and meanwhile, the catalyst has low loss rate of noble metal and good stability.

Detailed Description

The process of the present invention is described in detail below with reference to examples, but the examples are only illustrative and are not intended to limit the scope of the present invention.