CN105148935A - Catalyst for producing 2,3,4-trifluoroaniline and preparation method therefor and application thereof - Google Patents
Catalyst for producing 2,3,4-trifluoroaniline and preparation method therefor and application thereof Download PDFInfo
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Abstract
The invention provides a catalyst for continuously producing 2,3,4-trifluoroaniline. The catalyst contains an activated carbon carrier and Pt, metal M1 and metal M2 which are loaded on the activated carbon carrier, wherein the mass percentage of Pt in the catalyst is 0.1-1%, the mass percentage of the metal M1 in the catalyst is 0.05-1%, the mass percentage of the metal M2 in the catalyst is 0.05-2%, the metal M1 is Fe, Ru or Sn, and the metal M2 is K, Zn or Ce. The invention also provides a preparation method for the catalyst and a process for producing 2,3,4-trifluoroaniline through carrying out catalytic hydrogenation by using the catalyst. The catalyst provided by the invention has very high catalytic activity and stability, 2,3,4-trifluoronitrobenzene can be subjected to catalytic hydrogenation continuously, rapidly and efficiently so as to obtain 2,3,4-trifluoroaniline, and the reaction process is mild in conditions, high in production efficiency and easy in operation and is safe and environment-friendly, so that a good market popularization prospect can be achieved.
Description
Technical field
The invention belongs to the anti-dehalogenation technical field of catalytic hydrogenation, be specifically related to a kind of production 2,3,4-trifluoromethyl aniline Catalysts and its preparation method and application.
Background technology
2,3,4-trifluoromethyl aniline is a kind of important organic fine industrial chemicals and medicine intermediate, is mainly used in the industry such as medicine, agricultural chemicals, especially, on medical industry, it can be used for the carbostyril family antibacterial drugs such as synthesis Lomefloxacin, Norfloxacin, lavo-ofloxacin, Ofloxacin.Because such antibacterials have the significant advantages such as toxicity is low, duration of efficacy is long, side effect is little, make its application widely.Therefore, the global demand for 2,3,4-trifluoromethyl aniline is in and increases trend year by year, and market prospects are boundless.
, there is the problems such as cost is high, environmental pollution is large in the method that current China produces 2,3,4-trifluoromethyl aniline also backwardness relatively.China is mainly reducing agent with iron powder, and adopt reductase 12, the method for 3,4-trifluoronitrobenzene produces 2,3,4-trifluoromethyl aniline, but this reducing process can produce a large amount of iron mud, also can produce a large amount of containing amine waste water simultaneously, cause great harm to environment.So employing environmental protection, 2,3, the 4-of catalytic hydrogenating reduction method production efficiently trifluoromethyl aniline are trends of the times.Domestic have indivedual enterprise using batch tank catalytic hydrogenation process, but this technique exists problems such as operating cost is high, complicated operation, product purity are lower.
Therefore, the new technology that a kind of efficiency of research and development is high, safety and environmental protection produces 2,3,4-trifluoromethyl aniline is needed badly.
Summary of the invention
Technical problem to be solved by this invention is for above-mentioned the deficiencies in the prior art, provides a kind of and produces 2,3,4-trifluoromethyl aniline catalyst.This catalyst has very high catalytic activity and stability, can efficient catalytic Hydrogenation for 2,3,4-trifluoromethyl aniline, raw material 2,3, the conversion ratio of 4-trifluoronitrobenzene up to 100%, product 2,3, the productive rate of 4-trifluoromethyl aniline is greater than 99.5%, and defluorinate accessory substance ratio is less than 0.08%, and catalyst is not less than 2000h service life, and the catalytic efficiency of catalyst is high, the reaction velocity of 2,3,4-trifluoronitrobenzene is up to 0.5g/gcat/hr ~ 2g/gcat/hr.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of production 2,3,4-trifluoromethyl aniline catalyst, is characterized in that, comprise absorbent charcoal carrier and be carried on Pt, the metal M on described absorbent charcoal carrier
1and metal M
2, in described catalyst, the mass percentage of Pt is 0.1% ~ 1%, metal M
1mass percentage be 0.05% ~ 1%, metal M
2mass percentage be 0.05% ~ 2%, described metal M
1for Fe, Ru or Sn, described metal M
2for K, Zn or Ce.
Above-mentioned production 2,3,4-trifluoromethyl aniline catalyst, it is characterized in that, in described catalyst, the mass percentage of Pt is 0.3% ~ 0.8%, metal M
1mass percentage be 0.1% ~ 0.5%, metal M
2mass percentage be 0.2% ~ 0.9%.
Above-mentioned production 2,3,4-trifluoromethyl aniline catalyst, it is characterized in that, in described catalyst, the mass percentage of Pt is 0.45%, metal M
1mass percentage be 0.25%, metal M
2mass percentage be 0.5%.
Above-mentioned production 2,3,4-trifluoromethyl aniline catalyst, it is characterized in that, the shape of described absorbent charcoal carrier is graininess, the average grain diameter of described absorbent charcoal carrier is 1.5mm ~ 2.5mm, and the specific area of described absorbent charcoal carrier is 610m
2/ g ~ 1280m
2/ g.
In addition, present invention also offers a kind of method preparing above-mentioned catalyst, it is characterized in that, the method comprises the following steps:
Step one, the presoma of Pt is dissolved in nitric acid, obtains solution A after mixing, by metal M
1presoma be dissolved in nitric acid, obtain solution B after mixing, then solution A and solution B mixed, obtaining solution C, be immersed in solution C afterwards by absorbent charcoal carrier, is ultrasonic process 2h ~ 3h under the condition of 45 DEG C ~ 60 DEG C in temperature, nature cooled and filtered, obtains solid material D; The presoma of described Pt is chloroplatinic acid, described metal M
1presoma be metal M
1hydrochloride or metal M
1nitrate;
Step 2, the D of solid material described in step one is placed in drying box, first dry 3h ~ 5h under temperature is the condition of 50 DEG C ~ 70 DEG C, is then dry 3h ~ 5h under the condition of 90 DEG C ~ 110 DEG C in temperature, and obtaining load after naturally cooling has Pt and metal M
1catalyst precursor;
Step 3, by metal M
2presoma be dissolved in nitric acid, obtain solution E after mixing, then load described in step 2 had Pt and metal M
1catalyst precursor be immersed in solution E, be ultrasonic process 1h ~ 2h under the condition of 75 DEG C ~ 80 DEG C in temperature, natural cooled and filtered, obtains solid material F; Described metal M
2presoma be metal M
2hydrochloride or metal M
2nitrate;
Step 4, the F of solid material described in step 3 is placed in drying box, first dry 3h ~ 5h under temperature is the condition of 50 DEG C ~ 70 DEG C, is then dry 2h ~ 4h under the condition of 110 DEG C ~ 130 DEG C in temperature, and obtaining load after naturally cooling has Pt, metal M
1and metal M
2catalyst precursor;
Step 5, employing hydrogen have Pt, metal M to load described in step 4
1and metal M
2catalyst precursor carry out reduction treatment, obtain production 2,3,4-trifluoromethyl aniline catalyst.
Above-mentioned method, is characterized in that, described in step one and step 3, the mass percent concentration of nitric acid is 1.0% ~ 1.8%.
In addition, present invention also offers one and utilize above-mentioned catalyst to catalyzing hydrogenating to produce the method for 2,3,4-trifluoromethyl aniline, it is characterized in that, the method comprises the following steps:
Step one, by Catalyst packing in fixed bed reactors, then in the fixed bed reactors being filled with catalyst, pass into nitrogen, till by the air emptying in fixed bed reactors;
Step 2, activation process is carried out to the catalyst in the fixed bed reactors filled in step one after emptying air, obtain the catalyst after activating, the detailed process of described activation process is: the hydrogen passing into nitrogen dilution in fixed bed reactors, under the flow Q of the hydrogen of nitrogen dilution meets the condition of 20m≤Q≤25m, 0.5h ~ 1.5h is incubated after catalyst is first warming up to 70 DEG C ~ 90 DEG C with the heating rate of 2 DEG C/min ~ 3 DEG C/min, 1.5h ~ 2.5h is incubated after being warming up to 140 DEG C ~ 160 DEG C with the heating rate of 1 DEG C/min ~ 2 DEG C/min again, then 1.5h ~ 2.5h is incubated after being warming up to 210 DEG C ~ 230 DEG C with the heating rate of 0.5 DEG C/min ~ 1 DEG C/min, 40min ~ 50min is incubated after Temperature fall to 95 DEG C afterwards ~ 130 DEG C, described m is the quality of catalyst, and the unit of m is the unit of g, Q is mL/min,
Step 3, by 2,3,4-trifluoronitrobenzene, first alcohol and water by volume 1: (2 ~ 5): (0.25 ~ 0.5) mixes, obtain material liquid, then material liquid is preheated to 100 DEG C ~ 110 DEG C, hydrogen is preheated to 95 DEG C ~ 110 DEG C, afterwards the material liquid after preheating and the hydrogen after preheating are passed in the fixed bed reactors being filled with the catalyst after activation in step 2 and carry out catalytic hydrogenation reaction, obtain reactant liquor, finally reactant liquor is carried out condensation, gas-liquid separation and rectification process successively, obtain 2,3,4-trifluoromethyl aniline.
Above-mentioned method, is characterized in that, in the hydrogen of nitrogen dilution described in step 2, the volumn concentration of hydrogen is 30% ~ 40%, and surplus is nitrogen.
Above-mentioned method, is characterized in that, in hydrogen described in step 3 and material liquid, the mol ratio of 2,3,4-trifluoronitrobenzenes is (40 ~ 60): 1.
Above-mentioned method, is characterized in that, in the process of catalytic hydrogenation treatment described in step 3, the reaction velocity of 2,3,4-trifluoronitrobenzenes is 0.5g/gcat/hr ~ 2g/gcat/hr.
Adopt catalyst of the present invention to carry out to 2,3,4-trifluoronitrobenzene the reaction equation that catalytic hydrogenation generates 2,3,4-trifluoromethyl aniline to be:
The present invention compared with prior art has the following advantages:
1, catalyst of the present invention has very high catalytic activity and stability, can efficient catalytic Hydrogenation for 2,3,4-trifluoromethyl aniline, raw material 2, the conversion ratio of 3,4-trifluoronitrobenzene up to 100%, product 2,3, the productive rate of 4-trifluoromethyl aniline is greater than 99.5%, and defluorinate accessory substance is less than 0.08%, and catalyst is not less than 2000h service life.
2, the present invention adopts fixed bed reactors to produce 2,3,4-trifluoromethyl aniline, and 2,3,4-trifluoronitrobenzene continuous catalytic hydrogenation can be made to prepare 2,3,4-trifluoromethyl aniline, achieve the continuous prodution of 2,3,4-trifluoromethyl aniline, reaction condition is gentle, easily controls.
3, adopt catalyst of the present invention to carry out continuous catalytic hydrogenation process to 2,3,4-trifluoronitrobenzene and generate 2,3,4-trifluoromethyl aniline, catalytic efficiency is high, and feed stock conversion is high, and product yield is high, selective height, and simple to operate, energy consumption is low.
4, adopt the present invention to prepare 2,3,4-trifluoromethyl aniline, its conversion ratio and selective very high, accessory substance is few, and solvent can recycle, and can reach the zero-emission of pollutant, environmental protection.
5, process safety of the present invention is high, and operating cost is low, easily manipulates, and has good marketing prospect.
In a word, catalyst of the present invention has very high catalytic activity and stability, can make 2,3,4-trifluoronitrobenzene continuous catalytic hydrogenation generates 2,3,4-trifluoromethyl aniline, reaction condition is gentle, and production efficiency is high, personnel demand is few, easy to operate, safety and environmental protection, effectively can reduce by 2, the production cost of 3,4-trifluoromethyl aniline, has good marketing prospect.
Below in conjunction with embodiment, the present invention is described in further detail.
Detailed description of the invention
The present invention is produced 2,3,4-trifluoromethyl aniline Catalysts and its preparation method and is described by embodiment 1 to embodiment 10:
Embodiment 1
The present embodiment is produced 2,3,4-trifluoromethyl aniline catalyst and is comprised absorbent charcoal carrier and be carried on Pt, Fe and the K on absorbent charcoal carrier; In described catalyst, the mass percentage of the mass percent of Pt to be the mass percentage of 0.45%, Fe be 0.25%, K is 0.5%; The shape of described absorbent charcoal carrier is graininess, and its average grain diameter is 2.0mm, and specific area is 950m
2/ g.
The preparation method of the present embodiment catalyst comprises the following steps:
Step one, it is in the nitric acid of 1% that 1.1947g chloroplatinic acid (containing 0.45g platinum) is dissolved in 100mL mass percent concentration, solution A is obtained after mixing, be in the nitric acid of 1% by the 100mL mass percent concentration that is dissolved in of 0.7261g ferric trichloride (containing 0.25g iron), solution B is obtained after mixing, then solution A and B are mixed and obtain solution C, afterwards 98.8g absorbent charcoal carrier is immersed in solution C, submergence there is the solution C of absorbent charcoal carrier ultrasonic process 2.5h under temperature is the condition of 50 DEG C, nature cooled and filtered, obtain solid material D,
Step 2, the D of solid material described in step one is placed in drying box, first dry 4h under temperature is the condition of 60 DEG C, is then dry 4h under the condition of 100 DEG C in temperature, obtains the catalyst precursor that load has Pt and Fe after naturally cooling;
Step 3,0.9534g potassium chloride (containing 0.5g potassium) is dissolved in 200mL mass percent concentration is in the nitric acid of 1%, solution E is obtained after mixing, then the catalyst precursor of Pt and Fe there is is to be immersed in solution E load described in step 2, load submergence is had to have the solution E of the catalyst precursor of Pt and Fe ultrasonic process 1.5h under temperature is the condition of 78 DEG C, nature cooled and filtered, obtains solid material F;
Step 4, the F of solid material described in step 3 is placed in drying box, first dry 4h under temperature is the condition of 60 DEG C, is then dry 3h under the condition of 120 DEG C in temperature, obtains the catalyst precursor that load has Pt, Fe and K after naturally cooling;
Step 5, employing hydrogen have the catalyst precursor of Pt, Fe and K to carry out reduction treatment to load described in step 4, obtain production 2,3,4-trifluoromethyl aniline catalyst.
Embodiment 2
The present embodiment is produced 2,3,4-trifluoromethyl aniline catalyst and is comprised absorbent charcoal carrier and be carried on Pt, Fe and the K on absorbent charcoal carrier; In described catalyst, the mass percentage of the mass percent of Pt to be the mass percentage of 0.1%, Fe be 0.05%, K is 0.05%; The shape of described absorbent charcoal carrier is graininess, and its average grain diameter is 1.5mm, and specific area is 610m
2/ g.
The preparation method of the present embodiment catalyst comprises the following steps:
Step one, it is in the nitric acid of 1.5% that 0.2655g chloroplatinic acid (containing 0.1g platinum) is dissolved in 100mL mass percent concentration, solution A is obtained after mixing, be in the nitric acid of 1.5% by the 100mL mass percent concentration that is dissolved in of 0.1452g ferric trichloride (containing 0.05g iron), solution B is obtained after mixing, then solution A and B are mixed and obtain solution C, afterwards 99.8g absorbent charcoal carrier is immersed in solution C, submergence there is the solution C of absorbent charcoal carrier ultrasonic process 3h under temperature is the condition of 45 DEG C, nature cooled and filtered, obtain solid material D,
Step 2, the D of solid material described in step one is placed in drying box, first dry 4h under temperature is the condition of 60 DEG C, is then dry 4h under the condition of 100 DEG C in temperature, obtains the catalyst precursor that load has Pt and Fe after naturally cooling;
Step 3,0.09534g potassium chloride (containing 0.05g potassium) is dissolved in 200mL mass percent concentration is in the nitric acid of 1.5%, solution E is obtained after mixing, then the catalyst precursor of Pt and Fe there is is to be immersed in solution E load described in step 2, load submergence is had to have the solution E of the catalyst precursor of Pt and Fe ultrasonic process 1h under temperature is the condition of 75 DEG C, nature cooled and filtered, obtains solid material F;
Step 4, the F of solid material described in step 3 is placed in drying box, first dry 4h under temperature is the condition of 60 DEG C, is then dry 3h under the condition of 120 DEG C in temperature, obtains the catalyst precursor that load has Pt, Fe and K after naturally cooling;
Step 5, employing hydrogen have the catalyst precursor of Pt, Fe and K to carry out reduction treatment to load described in step 4, obtain production 2,3,4-trifluoromethyl aniline catalyst.
Embodiment 3
The present embodiment is produced 2,3,4-trifluoromethyl aniline catalyst and is comprised absorbent charcoal carrier and be carried on Pt, Fe and the K on absorbent charcoal carrier; In described catalyst, the mass percentage of the mass percent of Pt to be the mass percentage of 1.0%, Fe be 1.0%, K is 2.0%; The shape of described absorbent charcoal carrier is graininess, and its average grain diameter is 2.5mm, and specific area is 1280m
2/ g.
The preparation method of the present embodiment catalyst comprises the following steps:
Step one, 2.6548g chloroplatinic acid (containing 1.0g platinum) is dissolved in 80mL mass percent concentration is in the nitric acid of 1.8%, solution A is obtained after mixing, it is in the nitric acid of 1.8% that 2.9045g ferric trichloride (containing 1.0g iron) is dissolved in 80mL mass percent concentration, solution B is obtained after mixing, then solution A and B are mixed and obtain solution C, afterwards 96.0g absorbent charcoal carrier is immersed in solution C, submergence there is the solution C of absorbent charcoal carrier ultrasonic process 3h under temperature is the condition of 60 DEG C, nature cooled and filtered, obtains solid material D;
Step 2, the D of solid material described in step one is placed in drying box, first dry 3h under temperature is the condition of 70 DEG C, is then dry 3h under the condition of 110 DEG C in temperature, obtains the catalyst precursor that load has Pt and Fe after naturally cooling;
Step 3, be in the nitric acid of 1.8% by the 200mL mass percent concentration that is dissolved in of 3.8134g potassium chloride (containing 2.0g potassium), solution E is obtained after mixing, then the catalyst precursor of Pt and Fe there is is to be immersed in solution E load described in step 2, load submergence is had to have the solution E of the catalyst precursor of Pt and Fe ultrasonic process 1h under temperature is the condition of 75 DEG C, nature cooled and filtered, obtains solid material F;
Step 4, the F of solid material described in step 3 is placed in drying box, first dry 5h under temperature is the condition of 50 DEG C, is then dry 2h under the condition of 110 DEG C in temperature, obtains the catalyst precursor that load has Pt, Fe and K after naturally cooling;
Step 5, employing hydrogen have the catalyst precursor of Pt, Fe and K to carry out reduction treatment to load described in step 4, obtain production 2,3,4-trifluoromethyl aniline catalyst.
Embodiment 4
The present embodiment is produced 2,3,4-trifluoromethyl aniline catalyst and is comprised absorbent charcoal carrier and be carried on Pt, Fe and the Zn on absorbent charcoal carrier; In described catalyst, the mass percentage of the mass percent of Pt to be the mass percentage of 0.45%, Fe be 0.25%, Zn is 0.5%; The shape of described absorbent charcoal carrier is graininess, and its average grain diameter is 1.5mm, and specific area is 610m
2/ g.
The preparation method of the present embodiment catalyst comprises the following steps:
Step one, it is in the nitric acid of 1.2% that 1.1947g chloroplatinic acid (containing 0.45g platinum) is dissolved in 100mL mass percent concentration, solution A is obtained after mixing, it is in the nitric acid of 1.2% that 0.7261g ferric trichloride (containing 0.25g iron) is dissolved in 100mL mass percent concentration, solution B is obtained after mixing, then solution A and B are mixed and obtain solution C, afterwards 98.8g absorbent charcoal carrier is immersed in solution C, submergence there is the solution C of absorbent charcoal carrier ultrasonic process 2.5h under temperature is the condition of 50 DEG C, nature cooled and filtered, obtain solid material D,
Step 2, the D of solid material described in step one is placed in drying box, first dry 5h under temperature is the condition of 50 DEG C, is then dry 5h under the condition of 90 DEG C in temperature, obtains the catalyst precursor that load has Pt and Fe after naturally cooling;
Step 3,1.0424g zinc chloride (containing 0.5g zinc) is dissolved in 200mL mass percent concentration is in the nitric acid of 1.2%, solution E is obtained after mixing, then the catalyst precursor of Pt and Fe there is is to be immersed in solution E load described in step 2, load submergence is had to have the solution E of the catalyst precursor of Pt and Fe ultrasonic process 2h under temperature is the condition of 80 DEG C, nature cooled and filtered, obtains solid material F;
Step 4, the F of solid material described in step 3 is placed in drying box, first dry 5h under temperature is the condition of 50 DEG C, is then dry 4h under the condition of 110 DEG C in temperature, obtains the catalyst precursor that load has Pt, Fe and Zn after naturally cooling;
Step 5, employing hydrogen have the catalyst precursor of Pt, Fe and Zn to carry out reduction treatment to load described in step 4, obtain production 2,3,4-trifluoromethyl aniline catalyst.
Embodiment 5
The present embodiment is produced 2,3,4-trifluoromethyl aniline catalyst and is comprised absorbent charcoal carrier and be carried on Pt, Fe and the Zn on absorbent charcoal carrier; In described catalyst, the mass percentage of the mass percent of Pt to be the mass percentage of 0.8%, Fe be 0.1%, Zn is 0.9%; The shape of described absorbent charcoal carrier is graininess, and its average grain diameter is 2.0mm, and specific area is 980m
2/ g.
The preparation method of the present embodiment catalyst comprises the following steps:
Step one, 2.124g chloroplatinic acid (containing 0.8g platinum) is dissolved in 75mL mass percent concentration is in the nitric acid of 1.5%, solution A is obtained after mixing, it is in the nitric acid of 1.5% that 0.2905g ferric trichloride (containing 0.1g iron) is dissolved in 75mL mass percent concentration, solution B is obtained after mixing, then solution A and B are mixed and obtain solution C, afterwards 98.2g absorbent charcoal carrier is immersed in solution C, submergence there is the solution C of absorbent charcoal carrier ultrasonic process 3h under temperature is the condition of 45 DEG C, nature cooled and filtered, obtains solid material D;
Step 2, the D of solid material described in step one is placed in drying box, first dry 5h under temperature is the condition of 70 DEG C, is then dry 3h under the condition of 110 DEG C in temperature, obtains the catalyst precursor that load has Pt and Fe after naturally cooling;
Step 3,1.8763g zinc chloride (containing 0.9g zinc) is dissolved in 300mL mass percent concentration is in the nitric acid of 1.5%, solution E is obtained after mixing, then the catalyst precursor of Pt and Fe there is is to be immersed in solution E load described in step 2, load submergence is had to have the solution E of the catalyst precursor of Pt and Fe ultrasonic process 1.5h under temperature is the condition of 78 DEG C, nature cooled and filtered, obtains solid material F;
Step 4, the F of solid material described in step 3 is placed in drying box, first dry 3h under temperature is the condition of 50 DEG C, is then dry 4h under the condition of 130 DEG C in temperature, obtains the catalyst precursor that load has Pt, Fe and Zn after naturally cooling;
Step 5, employing hydrogen have the catalyst precursor of Pt, Fe and Zn to carry out reduction treatment to load described in step 4, obtain production 2,3,4-trifluoromethyl aniline catalyst.
Embodiment 6
The present embodiment is produced 2,3,4-trifluoromethyl aniline catalyst and is comprised absorbent charcoal carrier and be carried on Pt, Fe and the Zn on absorbent charcoal carrier; In described catalyst, the mass percentage of the mass percent of Pt to be the mass percentage of 0.3%, Fe be 0.5%, Zn is 0.2%; The shape of described absorbent charcoal carrier is graininess, and its average grain diameter is 1.5mm, and specific area is 610m
2/ g.
The preparation method of the present embodiment catalyst comprises the following steps:
Step one, it is in the nitric acid of 1% that 0.7965g chloroplatinic acid (containing 0.3g platinum) is dissolved in 100mL mass percent concentration, solution A is obtained after mixing, be in the nitric acid of 1% by the 200mL mass percent concentration that is dissolved in of 1.4523g ferric trichloride (containing 0.5g iron), solution B is obtained after mixing, then solution A and B are mixed and obtain solution C, afterwards 99.0g absorbent charcoal carrier is immersed in solution C, submergence there is the solution C of absorbent charcoal carrier ultrasonic process 2.5h under temperature is the condition of 50 DEG C, nature cooled and filtered, obtain solid material D,
Step 2, the D of solid material described in step one is placed in drying box, first dry 4h under temperature is the condition of 60 DEG C, is then dry 4h under the condition of 100 DEG C in temperature, obtains the catalyst precursor that load has Pt and Fe after naturally cooling;
Step 3,0.4169g zinc chloride (containing 0.2g zinc) is dissolved in 200mL mass percent concentration is in the nitric acid of 1%, solution E is obtained after mixing, then the catalyst precursor of Pt and Fe there is is to be immersed in solution E load described in step 2, load submergence is had to have the solution E of the catalyst precursor of Pt and Fe ultrasonic process 1h under temperature is the condition of 75 DEG C, nature cooled and filtered, obtains solid material F;
Step 4, the F of solid material described in step 3 is placed in drying box, first dry 4h under temperature is the condition of 60 DEG C, is then dry 3h under the condition of 120 DEG C in temperature, obtains the catalyst precursor that load has Pt, Fe and Zn after naturally cooling;
Step 5, employing hydrogen have the catalyst precursor of Pt, Fe and Zn to carry out reduction treatment to load described in step 4, obtain production 2,3,4-trifluoromethyl aniline catalyst.
Embodiment 7
The present embodiment is produced 2,3,4-trifluoromethyl aniline catalyst and is comprised absorbent charcoal carrier and be carried on Pt, Fe and the Ce on absorbent charcoal carrier; In described catalyst, the mass percentage of the mass percent of Pt to be the mass percentage of 0.45%, Fe be 0.25%, Ce is 0.5%; The shape of described absorbent charcoal carrier is graininess, and its average grain diameter is 1.5mm, and specific area is 610m
2/ g.
The preparation method of the present embodiment catalyst comprises the following steps:
Step one, 1.1947g chloroplatinic acid (containing 0.45g platinum) is dissolved in 80mL mass percent concentration is in the nitric acid of 1%, solution A is obtained after mixing, it is in the nitric acid of 1% that 0.8052g ferric nitrate (containing 0.25g iron) is dissolved in 80mL mass percent concentration, solution B is obtained after mixing, then solution A and B are mixed and obtain solution C, afterwards 98.8g absorbent charcoal carrier is immersed in solution C, submergence there is the solution C of absorbent charcoal carrier ultrasonic process 2.5h under temperature is the condition of 50 DEG C, nature cooled and filtered, obtains solid material D;
Step 2, the D of solid material described in step one is placed in drying box, first dry 4h under temperature is the condition of 60 DEG C, is then dry 4h under the condition of 100 DEG C in temperature, obtains the catalyst precursor that load has Pt and Fe after naturally cooling;
Step 3,1.5491g cerous nitrate (containing 0.5g cerium) is dissolved in 200mL mass percent concentration is in the nitric acid of 1%, solution E is obtained after mixing, then the catalyst precursor of Pt and Fe there is is to be immersed in solution E load described in step 2, load submergence is had to have the solution E of the catalyst precursor of Pt and Fe ultrasonic process 1h under temperature is the condition of 75 DEG C, nature cooled and filtered, obtains solid material F;
Step 4, the F of solid material described in step 3 is placed in drying box, first dry 4h under temperature is the condition of 60 DEG C, is then dry 3h under the condition of 120 DEG C in temperature, obtains the catalyst precursor that load has Pt, Fe and Ce after naturally cooling;
Step 5, employing hydrogen have the catalyst precursor of Pt, Fe and Ce to carry out reduction treatment to load described in step 4, obtain production 2,3,4-trifluoromethyl aniline catalyst.
Embodiment 8
The present embodiment is produced 2,3,4-trifluoromethyl aniline catalyst and is comprised absorbent charcoal carrier and be carried on Pt, Ru and the Ce on absorbent charcoal carrier; In described catalyst, the mass percentage of the mass percent of Pt to be the mass percentage of 0.45%, Ru be 0.25%, Ce is 0.5%; The shape of described absorbent charcoal carrier is graininess, and its average grain diameter is 2.5mm, and specific area is 1280m
2/ g.
The preparation method of the present embodiment catalyst comprises the following steps:
Step one, it is in the nitric acid of 1.6% that 1.1947g chloroplatinic acid (containing 0.45g platinum) is dissolved in 150mL mass percent concentration, solution A is obtained after mixing, it is in the nitric acid of 1.6% that 0.5131g ruthenic chloride (containing 0.25g ruthenium) containing 0.25g ruthenium is dissolved in 150mL mass percent concentration, solution B is obtained after mixing, then solution A and B are mixed and obtain solution C, afterwards 98.8g absorbent charcoal carrier is immersed in solution C, submergence there is the solution C of absorbent charcoal carrier ultrasonic process 2.5h under temperature is the condition of 50 DEG C, nature cooled and filtered, obtain solid material D,
Step 2, the D of solid material described in step one is placed in drying box, first dry 4h under temperature is the condition of 60 DEG C, is then dry 4h under the condition of 100 DEG C in temperature, obtains the catalyst precursor that load has Pt and Fe after naturally cooling;
Step 3,1.5491g cerous nitrate (containing 0.5g cerium) is dissolved in 200mL mass percent concentration is in the nitric acid of 1.6%, solution E is obtained after mixing, then the catalyst precursor of Pt and Ru there is is to be immersed in solution E load described in step 2, load submergence is had to have the solution E of the catalyst precursor of Pt and Ru ultrasonic process 1h under temperature is the condition of 75 DEG C, nature cooled and filtered, obtains solid material F;
Step 4, the F of solid material described in step 3 is placed in drying box, first dry 4h under temperature is the condition of 60 DEG C, is then dry 3h under the condition of 120 DEG C in temperature, obtains the catalyst precursor that load has Pt, Ru and Ce after naturally cooling;
Step 5, employing hydrogen have the catalyst precursor of Pt, Ru and Ce to carry out reduction treatment to load described in step 4, obtain production 2,3,4-trifluoromethyl aniline catalyst.
Embodiment 9
The present embodiment is produced 2,3,4-trifluoromethyl aniline catalyst and is comprised absorbent charcoal carrier and be carried on Pt, Sn and the Ce on absorbent charcoal carrier; In described catalyst, the mass percentage of the mass percent of Pt to be the mass percentage of 0.45%, Sn be 0.25%, Ce is 0.5%; The shape of described absorbent charcoal carrier is graininess, and its average grain diameter is 1.5mm, and specific area is 610m
2/ g.
The preparation method of the present embodiment catalyst comprises the following steps:
Step one, it is in the nitric acid of 1% that 0.7773g chloroplatinic acid (containing 0.45g platinum) is dissolved in 120mL mass percent concentration, solution A is obtained after mixing, it is in the nitric acid of 1% that 0.4752g stannous chloride (containing 0.25g tin) is dissolved in 120mL mass percent concentration, solution B is obtained after mixing, then solution A and B are mixed and obtain solution C, afterwards 98.8g absorbent charcoal carrier is immersed in solution C, submergence there is the solution C of absorbent charcoal carrier ultrasonic process 2.5h under temperature is the condition of 50 DEG C, nature cooled and filtered, obtain solid material D,
Step 2, the D of solid material described in step one is placed in drying box, first dry 4h under temperature is the condition of 60 DEG C, is then dry 4h under the condition of 100 DEG C in temperature, obtains the catalyst precursor that load has Pt and Fe after naturally cooling;
Step 3,1.5491g cerous nitrate (containing 0.5g cerium) is dissolved in 200mL mass percent concentration is in the nitric acid of 1%, solution E is obtained after mixing, then the catalyst precursor of Pt and Sn there is is to be immersed in solution E load described in step 2, load submergence is had to have the solution E of the catalyst precursor of Pt and Sn ultrasonic process 1h under temperature is the condition of 75 DEG C, nature cooled and filtered, obtains solid material F;
Step 4, the F of solid material described in step 3 is placed in drying box, first dry 4h under temperature is the condition of 60 DEG C, is then dry 3h under the condition of 120 DEG C in temperature, obtains the catalyst precursor that load has Pt, Sn and Ce after naturally cooling;
Step 5, employing hydrogen have the catalyst precursor of Pt, Sn and Ce to carry out reduction treatment to load described in step 4, obtain production 2,3,4-trifluoromethyl aniline catalyst.
Embodiment 10
The present embodiment is produced 2,3,4-trifluoromethyl aniline catalyst and is comprised absorbent charcoal carrier and be carried on Pt, Ru and the Zn on absorbent charcoal carrier; In described catalyst, the mass percentage of the mass percent of Pt to be the mass percentage of 0.45%, Ru be 0.25%, Zn is 0.5%; The shape of described absorbent charcoal carrier is graininess, and its average grain diameter is 1.5mm, and specific area is 610m
2/ g.
The preparation method of the present embodiment catalyst comprises the following steps:
Step one, 1.1947g chloroplatinic acid (containing 0.45g platinum) is dissolved in 75mL mass percent concentration is in the nitric acid of 1%, solution A is obtained after mixing, it is in the nitric acid of 1% that 0.5131g ruthenic chloride (containing 0.25g ruthenium) is dissolved in 75mL mass percent concentration, solution B is obtained after mixing, then solution A and B are mixed and obtain solution C, afterwards 98.8g absorbent charcoal carrier is immersed in solution C, submergence there is the solution C of absorbent charcoal carrier ultrasonic process 2.5h under temperature is the condition of 50 DEG C, nature cooled and filtered, obtains solid material D;
Step 2, the D of solid material described in step one is placed in drying box, first dry 4h under temperature is the condition of 60 DEG C, is then dry 4h under the condition of 100 DEG C in temperature, obtains the catalyst precursor that load has Pt and Ru after naturally cooling;
Step 3,1.0424g zinc chloride (containing 0.5g zinc) is dissolved in 200mL mass percent concentration is in the nitric acid of 1%, solution E is obtained after mixing, then the catalyst precursor of Pt and Ru there is is to be immersed in solution E load described in step 2, load submergence is had to have the solution E of the catalyst precursor of Pt and Ru ultrasonic process 1h under temperature is the condition of 75 DEG C, nature cooled and filtered, obtains solid material F;
Step 4, the F of solid material described in step 3 is placed in drying box, first dry 4h under temperature is the condition of 60 DEG C, is then dry 3h under the condition of 120 DEG C in temperature, obtains the catalyst precursor that load has Pt, Ru and Zn after naturally cooling;
Step 5, employing hydrogen have the catalyst precursor of Pt, Ru and Zn to carry out reduction treatment to load described in step 4, obtain production 2,3,4-trifluoromethyl aniline catalyst.
Catalyst of the present invention is utilized to be described by embodiment 11 to embodiment 14 method that 2,3,4-trifluoronitrobenzene carries out serialization catalytic hydrogenation production 2,3,4-trifluoromethyl aniline:
Embodiment 11
The catalyst that the present embodiment adopts is catalyst prepared by embodiment 1,2,3,4 or 5, and the method utilizing catalyst to catalyzing hydrogenating described in embodiment 1,2,3,4 or 5 to produce 2,3,4-trifluoromethyl aniline comprises the following steps:
Step one, by Catalyst packing in fixed bed reactors, then in the fixed bed reactors being filled with catalyst, pass into nitrogen, till by the air emptying in fixed bed reactors;
Step 2, activation process is carried out to the catalyst in the fixed bed reactors filled in step one after emptying air, obtain the catalyst after activating; The detailed process of described activation process is: the hydrogen passing into nitrogen dilution in fixed bed reactors, under the flow Q of the hydrogen of nitrogen dilution meets the condition of Q=20m, 0.5h is incubated after catalyst is first warming up to 90 DEG C with the heating rate of 2 DEG C/min, 1.5h is incubated after being warming up to 140 DEG C with the heating rate of 1 DEG C/min again, then be incubated 1.5h after being warming up to 210 DEG C with the heating rate of 0.5 DEG C/min, be incubated 40min after Temperature fall to 95 DEG C afterwards; Described m is the quality of catalyst, and the unit of m is the unit of g, Q is mL/min; In the hydrogen of described nitrogen dilution, the volumn concentration of hydrogen is 35%, and surplus is nitrogen;
Step 3, by 2, 3, 4-trifluoronitrobenzene, first alcohol and water mixes by volume at 1: 2: 0.25, obtain material liquid, then material liquid is preheated to 100 DEG C, hydrogen is preheated to 95 DEG C, afterwards the material liquid after preheating and the hydrogen after preheating are passed in the fixed bed reactors being filled with the catalyst after activation in step 2 and carry out catalytic hydrogenation reaction, to control in hydrogen and material liquid 2, 3, the mol ratio of 4-trifluoronitrobenzene is 40: 1, 2, 3, the reaction velocity of 4-trifluoronitrobenzene is 1.0g/gcat/hr, obtain reactant liquor, finally reactant liquor is carried out 0 DEG C of condensation successively, gas-liquid separation and rectification process, obtain 2, 3, 4-trifluoromethyl aniline.
Method described in embodiment 11 is utilized to produce the result of the test of 2,3,4-trifluoromethyl aniline in table 1.
Table 1
As shown in Table 1, utilize method described in embodiment 11 to produce 2,3,4-trifluoromethyl aniline, catalytic efficiency is high, and feed stock conversion is high, and product yield is high, and catalytic selectivity is high, long service life.
Embodiment 12
The difference of the present embodiment and embodiment 11 is only: described in step 2, material liquid is by 2,3,4-trifluoronitrobenzene, first alcohol and water mix form by volume at 1: 2: 0.5, and in the hydrogen of described nitrogen dilution, the volumn concentration of hydrogen is 30%, and surplus is nitrogen, in hydrogen described in step 3 and material liquid 2, the mol ratio of 3,4-trifluoronitrobenzene is 50: 1, described 2, the reaction velocity of 3,4-trifluoronitrobenzene is 0.5g/gcat/hr.
After testing, utilize method described in embodiment 12 to produce 2,3,4-trifluoromethyl aniline, catalytic efficiency is high, and feed stock conversion is high, and product yield is high, and catalytic selectivity is high, long service life.
Embodiment 13
The catalyst that the present embodiment adopts is catalyst prepared by embodiment 6,7,8,9 or 10, and the method utilizing catalyst to catalyzing hydrogenating described in embodiment 6,7,8,9 or 10 to produce 2,3,4-trifluoromethyl aniline comprises the following steps:
Step one, by Catalyst packing in fixed bed reactors, then in the fixed bed reactors being filled with catalyst, pass into nitrogen, till by the air emptying in fixed bed reactors;
Step 2, activation process is carried out to the catalyst in the fixed bed reactors filled in step one after emptying air, obtain the catalyst after activating; The detailed process of described activation process is: the hydrogen passing into nitrogen dilution in fixed bed reactors, under the flow Q of the hydrogen of nitrogen dilution meets the condition of Q=25m, 1.5h is incubated after catalyst is first warming up to 90 DEG C with the heating rate of 3 DEG C/min, 2.5h is incubated after being warming up to 160 DEG C with the heating rate of 2 DEG C/min again, then be incubated 2.5h after being warming up to 230 DEG C with the heating rate of 1 DEG C/min, be incubated 50min after Temperature fall to 130 DEG C afterwards; Described m is the quality of catalyst, and the unit of m is the unit of g, Q is mL/min; In the hydrogen of described nitrogen dilution, the volumn concentration of hydrogen is 36%, and surplus is nitrogen;
Step 3, by 2, 3, 4-trifluoronitrobenzene, first alcohol and water mixes by volume at 1: 5: 0.5, obtain material liquid, then material liquid is preheated to 110 DEG C, hydrogen is preheated to 110 DEG C, afterwards the material liquid after preheating and the hydrogen after preheating are passed in the fixed bed reactors being filled with the catalyst after activation in step 2, to control in hydrogen and material liquid 2, 3, the mol ratio of 4-trifluoronitrobenzene is 60: 1, 2, 3, the reaction velocity of 4-trifluoronitrobenzene is 1.0g/gcat/hr, obtain reactant liquor, finally reactant liquor is carried out 5 DEG C of condensations successively, gas-liquid separation and rectification process, obtain 2, 3, 4-trifluoromethyl aniline.
Method described in embodiment 13 is utilized to produce the result of the test of 2,3,4-trifluoromethyl aniline in table 2.
Table 2
As shown in Table 2, utilize method described in embodiment 13 to produce 2,3,4-trifluoromethyl aniline, catalytic efficiency is high, and feed stock conversion is high, and product yield is high, and catalytic selectivity is high, long service life.
Embodiment 14
The difference of the present embodiment and embodiment 13 is only: described in step 2, material liquid is by 2,3,4-trifluoronitrobenzene, first alcohol and water mix form by volume at 1: 3: 0.3, and in the hydrogen of described nitrogen dilution, the volumn concentration of hydrogen is 40%, and surplus is nitrogen, in hydrogen described in step 3 and material liquid 2, the mol ratio of 3,4-trifluoronitrobenzene is 45: 1, described 2, the reaction velocity of 3,4-trifluoronitrobenzene is 2.0g/gcat/hr.
After testing, utilize method described in embodiment 14 to produce 2,3,4-trifluoromethyl aniline, catalytic efficiency is high, and feed stock conversion is high, and product yield is high, and catalytic selectivity is high, long service life.
The above is only preferred embodiment of the present invention, not imposes any restrictions the present invention.Every above embodiment is done according to invention technical spirit any simple modification, change and equivalence change, all still belong in the protection domain of technical solution of the present invention.
Claims (10)
1. produce 2,3,4-trifluoromethyl aniline catalyst for one kind, it is characterized in that, comprise absorbent charcoal carrier and be carried on Pt, the metal M on described absorbent charcoal carrier
1and metal M
2, in described catalyst, the mass percentage of Pt is 0.1% ~ 1%, metal M
1mass percentage be 0.05% ~ 1%, metal M
2mass percentage be 0.05% ~ 2%, described metal M
1for Fe, Ru or Sn, described metal M
2for K, Zn or Ce.
2. production 2,3,4-trifluoromethyl aniline catalyst according to claim 1, it is characterized in that, in described catalyst, the mass percentage of Pt is 0.3% ~ 0.8%, metal M
1mass percentage be 0.1% ~ 0.5%, metal M
2mass percentage be 0.2% ~ 0.9%.
3. production 2,3,4-trifluoromethyl aniline catalyst according to claim 2, it is characterized in that, in described catalyst, the mass percentage of Pt is 0.45%, metal M
1mass percentage be 0.25%, metal M
2mass percentage be 0.5%.
4. production 2,3, the 4-trifluoromethyl aniline catalyst according to claim 1,2 or 3, it is characterized in that, the shape of described absorbent charcoal carrier is graininess, and the average grain diameter of described absorbent charcoal carrier is 1.5mm ~ 2.5mm, and the specific area of described absorbent charcoal carrier is 610m
2/ g ~ 1280m
2/ g.
5. prepare a method for catalyst as described in claim 1,2 or 3, it is characterized in that, the method comprises the following steps:
Step one, the presoma of Pt is dissolved in nitric acid, obtains solution A after mixing, by metal M
1presoma be dissolved in nitric acid, obtain solution B after mixing, then solution A and solution B mixed, obtaining solution C, be immersed in solution C afterwards by absorbent charcoal carrier, is ultrasonic process 2h ~ 3h under the condition of 45 DEG C ~ 60 DEG C in temperature, nature cooled and filtered, obtains solid material D; The presoma of described Pt is chloroplatinic acid, described metal M
1presoma be metal M
1hydrochloride or metal M
1nitrate;
Step 2, the D of solid material described in step one is placed in drying box, first dry 3h ~ 5h under temperature is the condition of 50 DEG C ~ 70 DEG C, is then dry 3h ~ 5h under the condition of 90 DEG C ~ 110 DEG C in temperature, and obtaining load after naturally cooling has Pt and metal M
1catalyst precursor;
Step 3, by metal M
2presoma be dissolved in nitric acid, obtain solution E after mixing, then load described in step 2 had Pt and metal M
1catalyst precursor be immersed in solution E, be ultrasonic process 1h ~ 2h under the condition of 75 DEG C ~ 80 DEG C in temperature, natural cooled and filtered, obtains solid material F; Described metal M
2presoma be metal M
2hydrochloride or metal M
2nitrate;
Step 4, the F of solid material described in step 3 is placed in drying box, first dry 3h ~ 5h under temperature is the condition of 50 DEG C ~ 70 DEG C, is then dry 2h ~ 4h under the condition of 110 DEG C ~ 130 DEG C in temperature, and obtaining load after naturally cooling has Pt, metal M
1and metal M
2catalyst precursor;
Step 5, employing hydrogen have Pt, metal M to load described in step 4
1and metal M
2catalyst precursor carry out reduction treatment, obtain production 2,3,4-trifluoromethyl aniline catalyst.
6. method according to claim 5, is characterized in that, described in step one and step 3, the mass percent concentration of nitric acid is 1.0% ~ 1.8%.
7. one kind utilizes catalyst to catalyzing hydrogenating as described in claim 1,2 or 3 to produce the method for 2,3,4-trifluoromethyl aniline, and it is characterized in that, the method comprises the following steps:
Step one, by Catalyst packing in fixed bed reactors, then in the fixed bed reactors being filled with catalyst, pass into nitrogen, till by the air emptying in fixed bed reactors;
Step 2, activation process is carried out to the catalyst filled in step one in the fixed bed reactors of emptying air, obtain the catalyst after activating, the detailed process of described activation process is: the hydrogen passing into nitrogen dilution in fixed bed reactors, under the flow Q of the hydrogen of nitrogen dilution meets the condition of 20m≤Q≤25m, 0.5h ~ 1.5h is incubated after described catalyst is first warming up to 70 DEG C ~ 90 DEG C with the heating rate of 2 DEG C/min ~ 3 DEG C/min, 1.5h ~ 2.5h is incubated after being warming up to 140 DEG C ~ 160 DEG C with the heating rate of 1 DEG C/min ~ 2 DEG C/min again, then 1.5h ~ 2.5h is incubated after being warming up to 210 DEG C ~ 230 DEG C with the heating rate of 0.5 DEG C/min ~ 1 DEG C/min, 40min ~ 50min is incubated after Temperature fall to 95 DEG C afterwards ~ 130 DEG C, described m is the quality of catalyst, and the unit of m is the unit of g, Q is mL/min,
Step 3, by 2,3,4-trifluoronitrobenzene, first alcohol and water by volume 1: (2 ~ 5): (0.25 ~ 0.5) mixes, obtain material liquid, then material liquid is preheated to 100 DEG C ~ 110 DEG C, hydrogen is preheated to 95 DEG C ~ 110 DEG C, afterwards the material liquid after preheating and the hydrogen after preheating are passed in step 2 in the fixed bed reactors being filled with activation rear catalyst and carry out catalytic hydrogenation treatment, obtain reactant liquor, finally reactant liquor is carried out condensation, gas-liquid separation and rectification process successively, obtain 2,3,4-trifluoromethyl aniline.
8. method according to claim 7, is characterized in that, in the hydrogen of nitrogen dilution described in step 2, the volumn concentration of hydrogen is 30% ~ 40%, and surplus is nitrogen.
9. method according to claim 7, is characterized in that, in hydrogen described in step 3 and material liquid, the mol ratio of 2,3,4-trifluoronitrobenzenes is (40 ~ 60): 1.
10. method according to claim 7, is characterized in that, in the process of catalytic hydrogenation treatment described in step 3, the reaction velocity of 2,3,4-trifluoronitrobenzenes is 0.5g/gcat/hr ~ 2.0g/gcat/hr.
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