CN1031663A - Amination Catalyst - Google Patents

Abstract

Al ₂ O ₃ as the main component of the ammoniation catalyst, one of which is δ- or θ- or any proportion of (δ+θ)-Al ₂ O ₃ supported Ni, Cu, Cr and/or Re active Composed of components, in which Al ₂ O ₃ is 65-90%, and the atomic ratio of the remaining active components is: Ni: Cu=1: 0.2-0.8, Ni: Cr=1: 0.0-0.5, Ni: Re= 1:0.001～0.01; the second is a compound of Ni, Cu, Cr, Ti and Al prepared by precipitation method, in which _Al2O3 is 63～32%, and the atomic ratio _of other active components is: Ni: Cu=1:1.0-2.0, Ni:Cr=1:0.1-0.5, Ni:Ti=1:1.0-2.0. The catalyst can be used in various ammoniation reactions, and is especially suitable for preparing morpholine, N-alkylmorpholine, aliphatic amine and N heterocyclic compounds.

Description

The present invention relates to a catalyst for ammoniation reaction, more specifically, the present invention relates to Al ₂ O ₃ and three or more metals or their oxides or their oxides selected from Ni, Cu, Cr, Ti and Re Mixture of ammoniation catalysts.

In the organic chemical industry, hydroxyl-containing compounds are often used, such as aliphatic monohydric or dihydric alcohols, especially diethylene glycol (DEG) or dialkylene glycol (DAG) or their derivatives for ammoniation to prepare Take aliphatic amines, morpholines, N-alkylmorpholines and other compounds to obtain a class of important chemical raw materials and products. The catalysts commonly used in the past are:

(1) Cu, Ni, Cr, Co, Mg, Mn, Pd, Pt, Rh, oxides of these metals or mixtures thereof [USP.3,151,112];

(2) 60-85% Ni, 14-37% Cu, 1-5% Cr (Mol.) [USP.3,152,998; USP.4,508,896];

(3) 0.2-5% Ru (wt.)/Al ₂ O ₃ [USP.3,155,357];

(4) Raney Ni-type catalyst [Special Publication No. 46-32188, -32189; Japanese Patent No. 50-99987; Japanese Patent No. 55-31781, -31782; DE2, 613, 344];

(5) 50-90% Ni, 9-45% Cu, 1-5% MoO ₃ [Special Publication No. 47-41908];

(6) 40-65%Ni, 15-40Cu, 1-10%Cr, 3-20%Al ₂ O ₃ (Mol.) [Special Publication 49-32699];

(7) 25-55% NiO, 15-40% CuO, 0.7-7% Cr ₂ O ₃ , 20-40% TiO ₂ (Wt) [SU.968,029];

(8) Ni, Co, Cr/γ-Al ₂ O ₃ [EP.0,036,331];

(9) CoO-CuO-Th or CoO-CuO-Ce [USP.4,532,324];

(10) Cu-Ni-Co/Al ₂ O ₃ [DE 3, 125, 662].

However, these known catalysts generally have defects such as high active metal content, easy pulverization, and excessive generation of intermediate diglycolamine (DGA) in the ammonolysis and cyclization reaction of diethylene glycol. , activity, selectivity and strength and other aspects still need to be improved. Therefore, it cannot be said to be completely satisfactory from the viewpoint of industrial application.

In recent years, it has been disclosed that morpholine (MOR) can be produced with DEG and NH ₃ using catalysts such as Ni and Re on γ- or α-Al ₂ O ₃ in batch-operated autoclave reactions, where , The Ni content relative to the weight of the carrier is: 2 to 20%. Other component content and reaction result are as follows:

(11) Ni-Cu-Cr-Re/α-Al ₂ O ₃ [JP-A-58-225078]:

Ni: Cu=1:0.4-0.02 (atomic ratio)

Ni:Cr=1:0.5-0.05 (atomic ratio)

Ni:Re=1:0.3-0.01 (atomic ratio)

DEG conversion rate: 58-60%

MOR selectivity: 32-35%

DGA selectivity: 51-55%

(12) Ni-Cr-Re/α-Al ₂ O ₃ [JP-A-59-4444]:

Ni:Cr=1:0.5-0.05 (atomic ratio)

Ni:Re=1:0.3-0.01 (atomic ratio)

DEG conversion rate: 70-79%

MOR selectivity: 40-50%

DGA selectivity: 36-47%

(13) Ni-Re/γ-Al ₂ O ₃ calcined at >900°C [JP-A-59-19543]:

Ni: Re = 1: 0.12-0.05 (atomic ratio)

DEG conversion rate: 88-92%

MOR selectivity: 58-63%

DGA selectivity: 24-31%

(14) Ni-Re-Er/γ-Al ₂ O ₃ [JP-A-59-115746]:

ZrO ₂ : 1-20wt% (relative to γ-Al ₂ O ₃ )

Ni: Re = 1: 0.01-0.3 (atomic ratio)

DEG conversion rate: 75-79%

MOR selectivity: 43-48%

DGA selectivity: 37-44%

This type of catalyst operates at a pressure of 200kg/cm ² (1.96×10 ⁷ Pa). Although it has good mechanical strength and stability, it still needs improvement in activity and selectivity. There are A large number of by-products are generated, and the utilization rate of raw materials is generally below 85%, which will inevitably reduce production efficiency in industrial applications.

In addition, in the general method of producing morpholine from DEG and NH ₃ , the reaction product usually contains 1-2% ether impurities, such as ethylene glycol, in addition to >20% (mol) of the intermediate product DGA Monomethyl ether (HOCH ₂ CH ₂ OCH ₃ ). Since this impurity is very close to the boiling point of MOR, it is not easy to remove it from the morpholine product. Such morpholine products would not be suitable for use as emulsifiers since it acts as a chain-stopper in the emulsion polymerization of synthetic rubber.

The object of the present invention is to obtain a kind of improved ammoniation catalyst, to overcome the above-mentioned shortcoming of existing catalyst.

Another object of the present invention is to use the catalyst with improved performance in the ammoniation reaction, improve the process method, increase the process efficiency and reduce the production cost.

Catalyst of the present invention has following characteristics:

In the amination reaction catalyst composed of Ni, Cu, Cr, Re and other metal elements or their oxides with Al ₂ O ₃ as the carrier, the carrier is δ-Al ₂ O ₃ or θ-Al ₂ O ₃ Or the mixture composed of the two in any proportion is obtained by roasting pseudo-boehmite at 750-920°C for 2-8 hours, the weight percentage of the carrier in the catalyst is 65-90, and the rest is the active component. The atomic ratios of each active component to Ni are: Ni:Cu=1:0.2-0.8, Ni:Cr=1:0.0-0.5, Ni:Re=1:0.001-0.01. The specific surface area of the alumina support is 50-200m ² /g, preferably 80-170m ² /g. The pore volume is 0.2-1.0ml/g, preferably 0.3-0.5ml/g. The loading of the active components can be carried out by sub-immersion or co-impregnation, and the impregnation solution can be any one of the corresponding salt solution, alcohol solution or ketone solution.

Another scheme of the catalyst of the present invention is: an ammoniation catalyst composed of a composite oxide of Ni, Cu, Cr, Ti and Al prepared by a precipitation method. Among them, the weight ratio of Al ₂ O ₃ in the catalyst is 63-32%, and the remaining components are 37-68%. According to the atomic ratio with Ni, they are: Ni:Cu=1:1.0-2.0, Ni:Cr=1 : 0.1 to 0.5, Ni: Ti = 1: 1.0 to 2.0. Its preparation method is to use the nitrates (such as Ni, Cu, Cr) and sulfates (such as Ti) of the above components to precipitate with Na ₂ CO ₃ according to the well-known method, and then dry and roast at 120-380°C. After crushing and sieving, it is kneaded with commercially available SB-aluminum hydroxide powder with water, extruded, then dried at 60-120°C and activated at 480°C. X-ray diffractometer It is determined that Al ₂ O ₃ is a γ-crystalline phase.

The catalyst of the present invention can be widely used in various ammoniation reactions, and is especially suitable for the production of fatty amines, mol In the reaction of morpholine and N-alkylmorpholine, this type of product can be represented by the following general formula:

In the formula, R ¹ , R ² , and R ³ may be the same or different, and each represents H or an alkyl group with 1-4 C atoms. R ⁴ represents H or substituted or unsubstituted 1-7C atom alkyl, aryl, cycloalkyl, saturated heterocyclic or acyl, etc. R ⁵ may be substituted or unsubstituted 1-18C atom alkyl, aryl, cycloalkyl or acyl.

In addition, the catalyst of the present invention can also be used to prepare five-membered or six-membered saturated N-heterocyclic compounds such as piperazine and piperidine from aliphatic dihydric alcohols.

The method for preparing the above-mentioned compound with the catalyst of the present invention is:

Under the pressure of 5×10 ⁵ ~ 6×10 ⁶ Pa (preferably 1.5 ~ 4.5×10 ⁶ Pa) and the temperature range of 160 ~ 300 ° C, the raw material (such _as DEG or DAG) and liquid ammonia are fed continuously from the top of the fixed-bed catalytic reaction device, keeping the liquid feed space velocity at 0.2-2.5hr ^-1 , the ratio of H ₂ to raw material at 1-10:1, ammonia and The ratio of the raw materials is between 1.5-8:1, and the morpholine compound or other ammonolysis reaction products are produced according to the trickle bed reaction mode.

The remarkable feature of the catalyst of the invention is that it has good mechanical strength and stability. It is in an autoclave containing liquid NH ₃ , DEG plus water, and the reaction generates water and hydrogen, at a pressure > 5.9×10 ⁶ Pa (60Kg/cm ² ), temperature: 200-220°C, and stirring speed: 200-400 At rpm, run for 5 hours each time, and then replace with new material. After 20 kettles of continuous reaction, the unloaded catalyst still maintains intact particles, and no pulverization occurs. In the continuous flow fixed-bed reactor, the accumulative feeding time was more than 1300 hours, and no damage was found on the catalyst particles.

Another notable feature of the catalyst of the present invention is that it has relatively high catalytic activity. For example, it can make DEG nearly completely (nearly 100%) ammonated, which can greatly increase productivity.

The remarkable feature of the catalyst of the present invention is that it has excellent selectivity. For example, it can make the converted DEG basically only produce the target product MOR, the formation of other impurities can be reduced to about 2% (mol), and the utilization rate of DEG is as high as 98% (mol), thus making product separation easy.

Another notable feature of the catalyst of the present invention is that it has high stability, that is, a long service life. For example, in the manufacture of morpholine, using the catalyst of the present invention, without using special regeneration technology, the cumulative feeding time is more than 1300 hours, and the DEG conversion rate and MOR single-pass yield can be maintained at 98% (mol) and 94% respectively. % above and remain unchanged, and there is still considerable operational potential.

The catalyst of the invention is used to carry out the ammoniation reaction, and the conversion rate of raw materials and the selectivity of products are greatly improved due to the excellent performance of the catalyst. Thereby, the product yield can be increased, the efficiency of the production process can be improved, and the production cost can be reduced.

The following are examples of catalysts of the present invention and their applications. Listed in the example is the result of using DEG as a raw material to carry out the ammonolysis cyclization reaction (a kind of amination reaction) in the presence of the catalyst of the present invention, but the catalyst of the present invention is not limited to this type of reaction.

Example 1

φ1.5mm strip-shaped θ-Al ₂ O ₃ (commercially available SB-aluminum hydroxide powder) with a specific surface area of 149m ² /g and a pore volume of 0.42ml/g (BET method). ℃ roasting for 4hr. The crystal phase was determined by X-ray diffractometer) 17 grams, with 19.5 grams of Ni (NO ₃ ) ₂ · 6H ₂ O, 3.8 grams of Cu (NO ₃ ) ₂ · 3H ₂ O and 6.6 grams of Cr ( NO ₃ ) ₃ ·9H ₂ O saturated solution impregnation in ethanol. Filter off the leaching solution, dry at 60°C, 2hr; 120°C, 4hr; 300°C, 2hr, then add a solution of 0.2ml perrhenic acid (HReO ₄ ) and water with a concentration of 38mgRe/ml (equal volume to the catalyst) ) impregnation. The leachate was filtered off, and after drying at 60° C. for 4 hr; 120° C. for 4 hr, the finished catalyst A was obtained. The chemical composition determined by plasma emission spectroscopy is: Al ₂ O ₃ :NiO (weight ratio)=12.5:1. The active component metal gram-atom ratio is:

Ni:Cu=1:0.26

Ni:Cr=1:0.32

Ni:Re=1:0.0023

The ammonolysis cyclization test of DEG was carried out on a common continuous flow fixed bed catalytic reaction device. Inner diameter 8mm, length 350mm, in the tubular reactor that is made by stainless steel, pack 4.8ml (3.6 grams) particle size and be 20-40 mesh catalyst A. At 300°C, after reducing for 3 hours with H ₂ flow at a pressure of 3-5×10 ⁵ Pa and a flow rate of 83ml/min, adjust the hydrogen pressure to 3×10 ⁶ Pa and the reaction temperature to 220°C. Next, under DEG:H ₂ (mol ratio)=1:8, according to the volumetric space velocity DEG=0.4hr ^-1 and DEG:NH ₃ (mol ratio)=1:10, use the pump to add DEG and Liquid _NH3 . The reaction products were determined with a gas chromatograph filled with a Porapak P column and a flame ionization detector.

The test results are shown in Table 1. The data showed high DEG conversion and MOR selectivity, and the single-pass yield of MOR was as high as 97% (mol).

Example 2

Catalyst B was prepared in the same way as in Example 1 except that it did not contain Cr components and the reaction temperature was 210°C. The composition of the catalyst is: Al ₂ O ₃ : NiO (weight ratio) = 7.7: 1, and the gram-to-atom ratio of the active component metal is:

Ni:Cu=1:0.61

Ni:Re=1:0.0045

The test results are also shown in Table 1. The data showed high DEG conversion activity and DEG utilization. However, the selectivity of cyclization is slightly low. In addition to the product being MOR, a certain amount of intermediate product DGA is also generated (DGA selectivity is about 11% mol).

Example 3

Catalyst C was prepared by combining 97.3 g Ni(NO ₃ ) ₂ 6H ₂ O, 121.5 g Cu(NO ₃ ) ₂ 3H ₂ O, 36.9 g Cr(NO ₃ ) ₃ 9H ₂ O and 84.1 g Ti ( SO ₄ ) ₂ was dissolved in 3 liters of warm water at 50°C and precipitated with Na ₂ CO ₃ ·10H ₂ O until the solution ^pH ≈8. Filtration and washing were repeated six times. After drying and roasting at 120°C and 380°C for 4 hours each, crush and sieve. Weigh 23 grams of dry rubber powder and 29 grams of commercially available SB-aluminum hydroxide powder, add water and knead evenly, and extrude into strips of φ1.5mm. After drying at 60°C for 3hr; 90°C for 3hr; 120°C for 3hr and activating at 480°C for 8.5hr, the finished catalyst Al ₂ O ₃ is a γ-phase, and its composition is: Al ₂ O ₃ : NiO=3.5: 1 (weight ratio), the metal gram-atom ratio of the active component is:

Ni:Cu=1:1.58

Ni:Cr=1:0.30

Ni:Ti=1:1.18

DEG ammonolysis cyclization test method, except that the reaction temperature is 235 ° C, the rest are the same as in Example 1. The results are also shown in Table 1. The data showed high MOR selectivity and DEG selectivity and DEG utilization, but slightly lower DEG conversion activity (DEG conversion was about 83%).

Example 4

The preparation method of catalyst D is: the φ1.5mm spherical (δ+θ)-Al ₂ O ₃ (aluminum sol method spherical hydrogen prepared by the Petrochemical Science Research Institute with a specific surface area of 159m ² /g and a pore volume of 1.0ml/g) Alumina was calcined at 870°C for 4hr) 8.3g, with 3.9g Ni(NO ₃ ) ₂ 6H ₂ O, 1.2g Cu(NO ₃ ) ₂ 3H ₂ O, 1.6g Cr(NO ₃ ) ₃ 9H ₂ O and 0.16ml HReO ₄ (concentration: 38mgRe/ml) and 6ml water impregnated. At 60°C, 3hr; 120°C, 3hr drying, and after 4hr activation at 400°C, the composition of the finished catalyst is: Al ₂ O ₃ : NiO (weight ratio) = 7.4: 1; the metal gram atom ratio of the active component for:

Ni:Cu=1:0.36

Ni:Cr=1:0.27

Ni:Re=1:0.0011

DEG ammonolysis cyclization test method is the same as that of Example 1. The reaction results are also given in Table 1. The data show that the same effect as that of catalyst A can be achieved by changing the precursor and crystal phase of the Al ₂ O ₃ carrier, and using the co-impregnation method of water immersion without immersion solution.

Table 1 (1) catalyst Reaction temperature, °C DEG conversion rate［2］，mol% MOR selectivity [3], mlo% DGA selectivity［4］mol% DEG utilization [5], mol% MOR one-way yield [6], mol% ABCD 220210235220 11099.3882.7998.52 96.8986.6695.4496.99 1.8610.921.02.0 98.7597.5896.4498.99 96.8986.1279.0195.55

〔1〕Data is the average value of six sampling analysis results during the reaction;

〔2〕DEG conversion rate (mol%)

= (moles of DEG consumed)/(moles of DEG fed) × 100%

〔3〕MOR selectivity (mol%)

= (moles produced by MOR)/(total moles of DEG conversion products) × 100%

〔4〕DGA selectivity (mol%)

= (moles produced by DGA)/(total moles of DEG conversion products) × 100%

〔5〕DEG utilization rate (mol%)

= MOR selectivity + DGA selectivity

〔6〕MOR one-way yield (mol%)

= DEG conversion rate × MOR selectivity

Example 5

Add 20 grams of Catalyst B after reduction at 300°C for 4 hours, 200 grams of DEG, and 193 grams of deionized water into a 1 liter stainless steel electromagnetically stirred autoclave, replace with H ₂ , and then add 48 grams of liquid NH ₃ . Then pressurize to ~3×10 ⁵ Pa with hydrogen, raise the temperature to 200°C and react for 4 hours. Catalyst composition, reaction conditions and the results of the ammonolysis cyclization test are shown in Table 2.

Comparative example 1

50ml of flaky α-Al ₂ O ₃ with a specific surface area of 1m ² /g, a diameter of 2 mm, and a length of 4 mm contains 16.15 g of Ni(NO ₃ ) ₂ ·6H ₂ O and 0.67 g of Cu(NO ₃ ) ₂ ·3H ₂ O , 4.45 g of Cr(NO ₃ ) ₃ ·9H ₂ O and 0.74 g of ammonium perrhenate (NH ₄ ReO ₄ ) were impregnated in 17 ml of an aqueous solution. After that, it was dried at 100 °C for 1 hr and reduced at 300 °C for 2 hr in _H2 atmosphere.

Add 15ml of the above catalyst and 150g of DEG into a 0.5l stainless steel electromagnetically stirred autoclave. After replacing with H ₂ , add 120 g of NH ₃ , pressurize to 2.65×10 ⁶ Pa with H ₂ , and raise the temperature to 240° C. for 2 hr.

The composition of the catalyst, the reaction conditions, and the reaction results calculated from the analysis of the reaction product liquid are also shown in Table 2.

Comparative example 2

Except that Ni on the catalyst is 8.4wt%, Ni: Cu=1:0.1, Ni: Cr=1:0.3 and Ni: Re=1:0.10, the rest are the same as Comparative Example 2. Reaction conditions and results are also shown in Table 3.

Table 2

Example 6

Starting from the φ1.5 spherical δ-Al ₂ O ₃ with a specific surface area of 120m ² /g and a pore volume of 0.79ml/g (produced by the lead sol process aluminum hydroxide produced by the No. Catalyst E prepared by embodiment 4 method, its chemical composition is:

Al ₂ O ₃ :NiO=3.5:1

Ni:Cu=1:0.23

Ni:Cr=1:0.14

Ni:Re=1:0.004

The physical and chemical data of the support and catalyst are shown in Table 3.

table 3

According to the method described in Example 1, catalyst E is at a reaction pressure of 2.94×10 ⁶ Pa, a temperature of 210-230°C, a volume space velocity of DEG=0.45hr ^-1 , DEG:H ₂ =1:6.2 and DEG:NH ₃ =1 Ammonolysis cyclization reaction test was carried out under the condition of 6.7 for 1300hr, until the late stage of the reaction, the data were respectively stable at the following levels.

DEG conversion rate (mol%): >99%

MOR selectivity (mol%): >94%

DGA selectivity (mol%): ~2%

DEG utilization rate (mol%): >96%

Example 7

According to the method of Example 6, the catalyst F prepared from the φ1.2mm clover-shaped strip δ-Al ₂ O ₃ with a specific surface area of 149m ² /g and a pore volume of 0.44ml/g, other chemical compositions are: Al ₂ O ₃ : NiO=5.6:1

Ni:Cu=1:0.35

Ni:Cr=1:0.30

Ni:Re=1:0.0044

The physicochemical data of the support and the catalyst are shown in Table 4.

Table 4

The synthesis test of N-ethylmorpholine (EtMOR) was carried out in the presence of catalyst F according to the method described in Example 1, except that the mixture of DEG and ethanol (EtOH) was used instead of pure DEG as the reaction feed. All the other reaction conditions and the test results calculated according to the gas chromatographic peak area are shown in Table 5.

table 5

^* Relative to transformed DEG.

Example 8

Except that the mixture of DEG and n-butanol (n-BuOH) (molecular ratio is 1:1) is used as the reaction feed instead of the mixture of DEG and ethanol, and H ₂ : DEG = 94: 1, NH ₃ : DEG = 1.9: 1, all the other are identical with embodiment 7. The product distribution based on the gas chromatographic peak area is shown in Table 6.

Table 6

The calculation results based on the DEG conversion products are as follows:

DEG conversion rate: 97.31%

BuMOR selectivity: 63.96%

MOR selectivity: 19.27%

DGA selectivity: 9.05%

DEG utilization rate: 92.28%

Formation rate of n-butylamine (n-BuNH ₂ ) based on remaining n-BuOH: 90.72%

Claims (8)

1. An amination reaction catalyst composed of Al ₂ O ₃ as a carrier supporting Ni, Cu, Cr, Re and other metals or their oxides, characterized in that the carrier is σ-Al ₂ O ₃ or Q- Al ₂ O ₃ or a mixture of the two in any proportion is obtained by roasting pseudo-boehmite at 750-920°C for 2-8 hours. The weight percentage of the carrier in the catalyst is 65-90, and the rest is active. Components; the amount of each active component in terms of atomic ratio to Ni is: Ni: Cu=1:0.2-0.8, Ni:Cr=1:0.0-0.5, Ni:Re=1:0.001-0.01. 2. The catalyst according to claim 1, wherein the alumina carrier has a specific surface area of 50-200m ² /g and a pore volume of 0.2-1.0ml/g. 3. The catalyst according to claim 1, characterized in that said alumina has a specific surface area of 80-170m ² /g and a pore volume of 0.3-0.5ml/g. 4. An ammoniation catalyst with Al ₂ O ₃ as its main component is characterized in that it is a composite oxide of Ni, Cu, Cr, Ti and Al prepared by a precipitation method, wherein Al ₂ O ₃ is a γ-phase, The weight percentage in the catalyst is 63～32, and the remaining components are 37～68. According to the atomic ratio with Ni, they are respectively: Ni: Cu=1: 1.0～2.0, Ni: Cr=1: 0.1～0.5, Ni: Ti=1:1.0-2.0. 5. According to the catalyst according to any one of claims 1, 2, 3 or 4, it is characterized in that it can be used in the reaction of producing a class of morpholine compounds with the general formula (I), wherein, R ¹ , R ² and ^R3 can be the same or different, and can be H or an alkyl group with 1-4C atoms, and ^R4 can be H or an alkyl group with 1-7C atoms, an aryl group or a cycloalkyl group.

6. The catalyst according to any one of claims 1, 2, 3 or 4 is characterized in that it can be used in the production of fatty amine R ⁵ NH ₂ . 7. The catalyst according to any one of claims 1, 2, 3 or 4, which can be applied to the reaction of producing saturated N heterocyclic compounds using HO(CH ₂ )nOH (n≥4) as raw material. 8. According to the said catalyst according to claim 1, 2 or 3, it is characterized in that its active components are loaded with any one of the corresponding salt aqueous solution or alcohol solution or ketone solution as the soaking liquid according to the mode of sub-immersion or co-impregnation on an Al ₂ O ₃ support.