阅读说明：本技术 制备芳族胺的催化剂体系 (Catalyst system for producing aromatic amines ) 是由 V·弗洛卡 D·加雷拉 M·赖泽尔 T·海德曼 H·德维尼 于 2020-04-01 设计创作，主要内容包括：本发明涉及一种适用于将芳族硝基化合物(I)氢化形成相应的芳族胺(II)的催化剂体系,该催化剂体系包含作为基本成分的：选自碳化硅、刚玉(α-Al-(2)O-(3))和微孔至无孔氧化锆(ZrO-(2))的组分A；和组分B,其包含B1选自二氧化硅、γ-、δ-或θ-氧化铝Al-(2)O-(3)、二氧化钛、二氧化锆和石墨的一种载体材料,B2选自铜、镍、钯、铂和钴的一种金属或多种金属,以及任选地B3选自至少一种选自元素周期表的I主族、II主族、IV主族和II副族、V副族、VI副族和VIII副族中的金属的其他金属,组分A的比例为5至60重量％,基于催化剂体系的总重量计,并且芳族硝基化合物(I)为通式R-(NO-(2))-(n)(I)中的那些,芳族胺(II)为通式R-(NH-(2))-(n)(II)中的那些,以及式(I)和(II)中的R部分和指数n具有以下含义：R为取代或未取代的芳族C-(6)-C-(10)部分,n为1至5的整数。(The present invention relates to a catalyst system suitable for hydrogenating aromatic nitro compounds (I) to form the corresponding aromatic amines (II), comprising as essential constituents: selected from silicon carbide and corundum (alpha-Al) 2 O 3 ) And microporous to nonporous zirconia (ZrO) 2 ) Component A of (1); and component B comprising B1 selected from the group consisting of silica, gamma, delta, or theta alumina Al 2 O 3 Titanium dioxide, zirconium dioxide and graphite, B2 being a metal or metals from the group consisting of copper, nickel, palladium, platinum and cobalt, and optionally B3 being at least one further metal from the group consisting of the metals of main group I, main group II, main group IV and subgroups II, V, VI and VIII of the periodic Table of the elements, the proportion of component A being from 5 to 60% by weight, based on the total weight of the catalyst system, and the aromatic nitro compound (I) being of the formula R- (NO) 2 ) n (I) Of (A), the aromatic amine (II) is of the formula R- (NH) 2 ) n Those of formula (II), as well as the R moieties and the index n in formulae (I) and (II), have the following meanings: r is a substituted or unsubstituted aromatic C 6 ‑C 10 And n is an integer of 1 to 5.)

1. A catalyst system suitable for hydrogenating aromatic nitro compounds (I) to form the corresponding aromatic amines (II), comprising as essential constituents a component A selected from the group consisting of silicon carbide, corundum (. alpha. -Al), and a component B₂O₃) And microporous to nonporous zirconia (ZrO)₂) Said component B comprising Al selected from silica, gamma-, delta-or theta-alumina₂O₃Titanium dioxide, zirconium dioxide and graphite, a support material B1 of a metal or metals B2 selected from copper, nickel, palladium, platinum and cobalt, and optionally at least one further metal B3 selected from the group of the metals of main group I, main group II, main group IV and subgroups II, V, VI and VIII of the periodic Table of the elements, wherein the proportion of component A is from 5 to 60% by weight, based on the total weight of the catalyst system, and wherein the aromatic nitro compound (I) is of the formula R- (NO)₂)_nThose of (I), the aromatic amine (II) being of the formula R- (NH)₂)_nThose of formula (I), (II) and the R moiety and the index n in formulae (I) and (II) have the following meanings: r is a substituted or unsubstituted aromatic C₆-C₁₀And n is an integer of 1 to 5.

2. The catalyst system of claim 1, wherein component a is a constituent of component B1.

3. The catalyst system according to claims 1 to 2, wherein component a comprises silicon carbide.

4. The catalyst system according to claims 1 to 3, wherein component A comprises only silicon carbide.

5. The catalyst system of claims 1 to 4, wherein component B2 comprises copper.

6. The catalyst system of claims 1-5, wherein component B2 comprises copper only.

7. The catalyst system of claims 1-6, wherein component A comprises only silicon carbide and component B2 comprises only copper.

8. The catalyst system of claims 1 to 7, wherein component A is a constituent of component B1, and component A comprises only silicon carbide, and component B2 comprises only copper.

9. A process for preparing the catalyst system of claims 1 to 8 by the following steps

i) Preparation of Al containing a compound selected from the group consisting of silica, gamma-, delta-or theta-alumina₂O₃Titanium dioxide, zirconium dioxide and graphite, and with one or more metals B2 selected from copper, nickel, palladium, platinum and cobalt, and optionally with B3 selected from at least one metal selected from the group consisting of the metals of main group I, main group II, main group IV and subgroup II, subgroup V, subgroup VI and subgroup VIII of the periodic Table of the elements, and with silicon carbide, corundum (. alpha. -Al)₂O₃) And low to non-porous zirconia (ZrO)₂) Component A of (A) in combination, or

ii) preparation of Al containing iia) selected from silica, gamma-, delta-or theta-alumina₂O₃Titanium dioxide, zirconium dioxide and graphite and a component selected from the group consisting of silicon carbide, corundum (. alpha. -Al)₂O₃) And low to non-porous zirconia (ZrO)₂) Component A, and contacting the support material with one or more metals B2 selected from the group consisting of copper, nickel, palladium, platinum and cobalt, and optionally with at least one metal selected from the group consisting of main group I, main group II, main group IV and subgroup II, subgroup II of the periodic Table of the elementsB3 of at least one metal of group V, subgroup VI and subgroup VIII.

10. A catalyst system obtainable by the process of claim 9.

11. Use of the catalyst system according to claims 1 to 10 for preparing the aromatic amines (II) according to claim 1 by hydrogenation of the aromatic nitro compounds according to claim 1.

12. Process for the preparation of aromatic amines (II) according to claim 1 by catalytic hydrogenation of the corresponding aromatic nitro compounds (II) according to claim 1, characterized in that catalyst systems according to claims 1 to 10 are used.

13. The process of claim 12, wherein the process is carried out in a fluidized bed.

14. The process according to claims 12 to 13, wherein the aromatic amine compound (II) is aniline and the corresponding aromatic nitro compound (I) is nitrobenzene.

Examples

Silicon carbide is also known as SiC. Silicon dioxide is also known as SiO₂。

The parameters were determined as follows:

the particle size distribution was measured by laser diffraction on a Malvern Mastersizer according to ISO 13320.

Average particle diameter (d)₅₀Values) were calculated from the particle size distribution (see above).

BET surface area is in accordance with DIN 66131.

Pore volume (porosity) in accordance with DIN 66133.

k value

The heat transfer in the form of k-value for the catalyst system of the invention and the comparative catalyst was measured as follows: one liter of catalyst was fluidized with nitrogen in a fluidized bed reactor. A heating probe having a known surface area a is used to heat the fluidized catalyst to a specified temperature difference deltat relative to the heating probe temperature. The k value of the catalyst sample can then be determined by the required electrical heating power P.

Wear and tear

The monteatini attrition test simulates the mechanical loading on the fluidized material (in this case the catalyst system of the present invention) in a fluidized bed. The wear device consists of a nozzle plate with a nozzle diameter of 0.5mm and which is connected in a gas-tight and solid manner to a glass column element (diameter 30 mm). A conically widening steel tube is connected to the upper part of the glass column element in an equally gas-tight and solid manner. The system was connected to a nitrogen source at 10 bar. The pressure reducer was used to adjust the supply pressure to 6bar for operation. The system was run under ambient conditions without overpressure.

60.0g of the bulk material under investigation (in this case the catalyst system of the invention) was introduced into the apparatus. The gas volume flow for fluidization was set at 350 l/h. The high gas velocity at the nozzle causes particle attrition or breakage through particle-particle and particle-wall contact. The discharged solid enters the filter paper sleeve through the bent pipe. The discharged material was weighed after one hour and after five more hours to determine the fines content (after 1 h) and the attrition (after 5 h).

Expansion of

The glass fluidized bed apparatus (QVC standard tube, length 500mm, diameter 50mm) was connected to a nitrogen source (10 bar). The apparatus was filled with 200g of particles and gas was passed into the product by opening the ball valve in the feed line. After the particles are thoroughly mixed (20-30s), the ball valve is closed quickly. Once all bubbles have left the particle layer, a bubble-free fluidized bed is formed and the bed height is recorded immediately. This corresponds to the height of the expanded fluidized bed without bubbles. Thereafter the bed height continues to slowly decrease due to further loss of gas until the endpoint is reached. This corresponds to the settled bed height, which is also recorded. Expansion is defined as the ratio of the height of the expanded bed to the height of the settled bed.

Example 1: made of SiC and SiO₂Preparation of support Material B1

13.5% by weight of an aqueous suspension (80% by weight of SiO) were spray-dried in a spray tower at a nozzle pressure of 1.8bar₂(hydrogel D11-20, BASF, ground to 10 μm) and 20% by weight of SiC (SC53232 powder, Saint Gobain NorP)ro)) and 0.5% by weight of NaOH is added, a carrier material consisting of silicon carbide and silicon dioxide is sprayed to a solid, pulverulent product. After screening off the fine fraction, a mixed support is obtained having a BET specific surface area of 297m²G, Hg pore volume of 1.16ml/g, d₅₀The value was 52 μm.

Example 2: preparation of a copper-containing catalyst System

150g of a powdery catalyst support 2016750030(Saint Gobain NorPro, pore volume 0.69ml/g) consisting of silicon carbide and silicon dioxide in a mass ratio of 30:70 was placed in a rotary evaporator. 50g of an ammonia solution of Cu (15% by weight CuO, density d 1.244g/l) were added to the support at 120 ℃ and 480 mbar. In further six impregnation steps an additional 240.3g of Cu solution was added. After each impregnation step, the material was dried at 120 ℃ and 480mbar for 1h, and in the last two impregnation steps, the material was dried at 120 ℃ and 300mbar for 2 h. The product was forced through a 250 μm sieve to break up the agglomerates that had formed. The catalyst was then finally heated to 390 ℃ in a muffle furnace at a rate of 1K/min and calcined at 390 ℃ for 2 h. The catalyst system has a CuO content of 22.2 wt.% and comprises particles having an average particle diameter (d)₅₀Value) was 114 μm.

Example 3: preparation of a copper-containing catalyst System

The mass ratio of the components is 30: 70.5 kg of a pulverulent catalyst support 2016750030 consisting of silicon carbide and silicon dioxide (Saint Gobain NorPro, pore volume 0.69ml/g) were placed in a roller dryer and heated to 80 ℃. An ammonia solution of Cu (14% by weight CuO, density d 1.205g/l) was sprayed in6 portions of 1.14kg (6.87 kg in total) and the material was dried in a tumble dryer at 80 ℃ for 45min between the various impregnation steps. 100ml of 25% NH was used for the nozzle₃The solution is washed clean. After all impregnation solution had been added, the catalyst was dried at 80 ℃ for 5h until the pressure obtained<100 mbar. The catalyst was then finally heated to 550 ℃ in a muffle furnace at a rate of 1K/min and calcined at 550 ℃ for 2 h. The catalyst data are shown in the table.

Example 4: preparation of a catalyst without SiC (comparative)

Mixing powdery SiO₂The support (BV0308, BASF) was impregnated with an ammonia-containing Cu solution, dried and finally calcined in a similar manner to example 2. The catalyst had a CuO content of 21.2 wt.% and contained particles having an average particle diameter (d)₅₀Value) was 112 μm.

Example 5: preparation of another catalyst without SiC (comparative)

Powdery SiO₂The support (BV0308, BASF) was impregnated with an ammonia-containing Cu solution, dried and finally calcined in a similar manner to example 3. The catalyst data are shown in the table.

Example 6: preparation of anilines

The SiC-SiO-containing material prepared in example 3 was examined in continuous operation as follows₂Performance of supported Cu-containing catalyst system and performance of non-inventive catalyst from example 5: the preheated nitrobenzene was pumped through a two-phase nozzle into a 5l fluidized-bed reactor, where it was fluidized by a partial stream of hydrogen at the nozzle opening. The reaction is carried out at a temperature of 290 ℃ and a pressure of 5bar (6bar abs.) with a duration of 2Nm³Hydrogen,/h and 8Nm³Nitrogen per hour and nitrobenzene per hour 1.2 kg/hour.

100% conversion and 99.7% aniline selectivity were achieved using 2.2kg of the catalyst system of example 3. The catalyst can be fully regenerated by intermediate regeneration with an air/nitrogen mixture at 220-290 ℃ and also shows 100% conversion and 99.7% aniline selectivity in the 2 nd to 6 th cycle. Then the experiment was ended, the catalyst still remained active. No copper coating was observed in the unloaded catalyst.

The results are summarized in the table below.

Table: aniline preparation

The parameters listed in the table were determined as described above.

It has surprisingly been found that SiO containing SiC₂The support can still be easily doped with Cu in the order of 20 wt.%, even if the support is modifiedLess pore volume is available for impregnation. This is surprisingly not accompanied by an adverse effect on the conversion behavior and selectivity of the catalyst system of the invention.

Based on SiO containing SiC₂The powdered catalyst system of the present invention surprisingly achieves a disproportionately high BET surface area. The heat transfer behavior (k-value) of the catalyst system of the invention is far superior to that of the comparative catalyst.