CN109999856B - Catalyst for synthesizing 2, 2-difluoroethylamine and preparation method and application thereof - Google Patents
Catalyst for synthesizing 2, 2-difluoroethylamine and preparation method and application thereof Download PDFInfo
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- CN109999856B CN109999856B CN201910347875.1A CN201910347875A CN109999856B CN 109999856 B CN109999856 B CN 109999856B CN 201910347875 A CN201910347875 A CN 201910347875A CN 109999856 B CN109999856 B CN 109999856B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
- B01J27/25—Nitrates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/22—Halogenating
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/08—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
Abstract
The invention relates to a catalyst for synthesizing 2, 2-difluoroethylamine, a preparation method and application thereof, and belongs to the technical field of chemical industry. Weighing one or more of alkali metal salt and rare earth metal salt as active components, preparing impregnation liquid according to a certain proportion, adding a catalyst carrier after dissolution is finished, standing and impregnating for 12-24 hours; filtering the impregnated catalyst, drying at 80-250 ℃ for 12-36h, roasting at 300-550 ℃ for 12-36h to obtain a catalyst precursor, then carrying out bromination reaction by using hydrogen bromide, and controlling the mass content proportion of oxygen elements in the active components of the catalyst to finally obtain the catalyst for the ammoniation reaction. The ammoniation catalyst is particularly suitable for the gas phase continuous reaction process for preparing 2, 2-difluoroethylamine by ammoniating 2, 2-difluoro-1-chloroethane, and has the advantages of low requirement on equipment, low production cost, high reaction activity and high selectivity of a target product.
Description
Technical Field
The invention relates to a catalyst, a preparation method thereof and application thereof in preparing 2, 2-difluoroethylamine through gas-phase reaction.
Background
2, 2-difluoroethylamine is an important fluorine-containing aliphatic compound, can be used as a raw material or an intermediate for synthesizing products such as medicines, pesticides and the like, and has important industrial value. The 2, 2-difluoroethylamine derivatives are useful as effective intermediates for the preparation of pesticidal actives. For example, suitable amine difluorohexanoates derivatives can be used to synthesize carbonyl compounds, such as 4-amino-2-butyrate compounds, by converting the amino group into an insecticidally active ingredient. Meanwhile, the method can be used as an effective intermediate for preparing integrated circuits in the liquid crystal display industry.
The synthesis route of 2, 2-difluoroethylamine mainly comprises seven routes: 1) swarts takes 1-bromo-2, 2-difluoroethane as a starting material, and the mixture is heated and reacted for 72 hours in a test tube filled with 2mol of ammonium acetate at the temperature of 125-145 ℃, and the reactants are completely converted into the compounds of difluoroethylamine and tetrafluoroethylamine. But has the disadvantages of long reaction period and poor reaction selectivity; 2) kluger takes amide boron trifluoride diethyl etherate complex as raw material to synthesize 2, 2-difluoroethylamine, but the raw material is expensive and not easy to obtain, the byproduct is difficult to treat, and the industrialization difficulty is large. 3) Patents CN102741218, US2011166388 and US8242311 report a process route for synthesizing 2, 2-difluoroethylamine by using difluoroacetonitrile as a starting material, but the catalyst is expensive and cannot be recycled, and the process involves acidification treatment, so that three wastes are more, and the difficulty of post-treatment is increased. 4) Patent US20110082318 and patent WO2011042376 report methods for synthesizing 2, 2-difluoroethylamine by catalytic hydrogenation of 1, 1-difluoro-2-nitroethane, and the methods have the disadvantages that the catalyst is difficult to recycle, the hydrogenation reaction needs high-temperature and high-pressure conditions, and the requirements on equipment are high. 5) CN104030928 reports that 2, 2-difluoroethanol is used as a starting material, hydrogen and ammonia are mixed to react in a fixed bed reactor, and continuous production is easy, but the raw material 2, 2-difluoroethanol and a noble metal catalyst are expensive and the production cost is high. 6) Dickey describes the use of 2, 2-difluoro-1-chloroethane and 28% ammonia as starting materials, and the autoclave reaction is adopted, the preparation method has a long reaction period, and the reaction mixture can cause corrosion to equipment under high temperature conditions, thereby reducing the service life of the reaction kettle. 7) Patents US 20184777, CN103370290, CN102471229, US8188319 and US20110060167 all report that 2, 2-difluoro-1-chloroethane and liquid ammonia are used as starting materials, a solvent and a catalyst are selectively used, and the reaction is carried out in a high-pressure container.
In the above synthetic route, 2-difluoro-1-chloroethane and liquid ammonia are used as starting materials, which has obvious advantages in raw material price compared with other reaction routes, and in order to avoid using solvents and operating conditions such as high-pressure reaction vessels in the reaction process and reduce the three wastes and equipment use requirements, a novel catalyst needs to be developed, and a fixed bed reactor is adopted to prepare 2, 2-difluoroethylamine through gas phase reaction, so that the method is suitable for industrial production.
Disclosure of Invention
Aiming at the defects of the process, the invention provides the catalyst for synthesizing the 2, 2-difluoroethylamine, which has the advantages of simple preparation process, high selectivity of target products, suitability for gas-phase continuous reaction, high reaction efficiency and the like, and can meet the requirements of industrial application.
The technical scheme adopted by the invention is as follows:
a method for preparing an ammoniation catalyst comprising the sequential steps of:
(1) weighing alkali metal salt as a main active component, or weighing alkali metal salt as a main active component and rare earth metal salt as an auxiliary component, adding absolute ethyl alcohol to prepare impregnation liquid, adding a catalyst carrier after dissolution is finished, and standing for impregnation;
(2) filtering, drying and roasting the impregnated catalyst at high temperature;
(3) the catalyst precursor after roasting is placed in a reaction tube, a certain amount of hydrogen bromide is introduced, and the reaction is carried out at the temperature of 150-.
The mass content of the oxygen element is preferably 7-12%.
The active component loading amount is 10-30%, and the concentration of the impregnation liquid is 0.1-1 mol/L.
The catalyst carrier is coconut shell activated carbon with the micropore number of 700-750m2Per g, specific surface area greater than 1000m2/g。
The alkali metal salt and the rare earth metal salt are soluble halide, nitrate, sulfate, carbonate, acetate and double salt.
The alkali metal salt is sodium nitrate or potassium nitrate, the rare earth metal salt is lanthanum nitrate, and the mass ratio of the alkali metal salt to the rare earth metal salt is 1: 1.
the standing and dipping time is 12-24h, the drying is carried out for 12-36h at the temperature of 80-250 ℃, the roasting is carried out for 12-36h at the temperature of 300-550 ℃,
preferably: the drying temperature is preferably 80-200 ℃, and the time is preferably 12-24 hours; the roasting temperature is preferably 400-500 ℃, and the time is preferably 12-24 h.
The ammoniation catalyst prepared by the method.
The ammoniation catalyst is applied to the reaction of preparing 2, 2-difluoroethylamine by continuously ammoniating 2, 2-difluoro-1-chloroethane in a gas phase.
The conditions of the gas-phase continuous ammoniation reaction are as follows: an ammoniation catalyst is filled in the fixed bed reactor, the reaction pressure is 0.1-0.15 MPa, the reaction temperature is 100-180 ℃, and the molar ratio of 2, 2-difluoro-1-chloroethane to ammonia gas is 1: 6-10; 2, 2-difluoro-1-chloroethane and ammonia gas total space velocity of 10-150h-1。
The reaction temperature is 140 ℃ and 180 ℃, and the molar ratio of the 2, 2-difluoro-1-chloroethane to the ammonia gas is 1: the total space velocity of 8, 2, 2-difluoro-1-chloroethane and ammonia gas is 10-50h-1。
One of the reactants is ammonia, which is easy to destroy or neutralize L acid center of the catalyst, and the oxygen content is limited so that the catalyst keeps a certain amount of hypobromite, so that the acid center of the catalyst is more stable than a pure bromide salt even if the acid center of the catalyst is destroyed by the ammonia, but the content of the hypobromite is not too high, so that the acidity of the catalyst is too high, ammonium salt formed after the ammonia is neutralized can cover the surface of the catalyst, the specific surface area of the catalyst is reduced, and finally the catalyst is deactivated.
The reaction is a micro-positive pressure (0.1-0.15 MPa) gas phase continuous reaction, and the feeding amount and the contact time can be calculated after the total airspeed and the material ratio are limited.
Compared with the prior art, the method has the advantages that micro-positive pressure (0.1-0.15 MPa) continuous reaction is realized, the equipment requirement is low, and the operation is simple; the selectivity and the yield of the target product are high; organic solvent is not used, and three wastes are less; the contact time is short (the contact time is 1.2min in example 7), and the production efficiency is high.
The invention has the advantages of
1) The catalyst has simple preparation process and good repeatability;
2) the catalyst has high specific surface area and high selectivity of target products;
3) the catalyst of the invention has good stability in the reaction of synthesizing 2, 2-difluoroethylamine.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention to these embodiments.
Example 1 (sample 1)
In a total loading of 20% (as KNO)3Design) weighing KNO3Adding anhydrous ethanol to the powder to prepare an impregnation solution, and adding a certain amount of coconut shell activated carbon (the number of micropores of the carrier is 700-2Per g, specific surface area greater than 1000m2And/g) standing and soaking for 12 h. Filtering the impregnated catalyst, drying at 80 ℃ for 12h, and roasting at 500 ℃ for 12 h;
385ml of the roasted catalyst precursor is placed in a reaction tube, 50ml/min of hydrogen bromide is introduced at the temperature of 150 ℃, the introduction time is 45min, and the XPS analysis is used for analyzing that the mass content of oxygen accounts for 8.2 percent of the active component.
Example 2 (sample 2)
In a total loading of 20% (as NaNO)3Design) weighing NaNO3Adding anhydrous ethanol to the powder to prepare an impregnation solution, and adding a certain amount of activated carbon carrier (the carrier has the micropore number of 700-750 m) after all the metal salts are completely dissolved2Per g, specific surface area greater than 1000m2And/g) standing and soaking for 24 hours. Filtering the impregnated catalyst, drying at 100 ℃ for 24h, and roasting at 400 ℃ for 24 h;
385ml of the roasted catalyst precursor is placed in a reaction tube, 50ml/min of hydrogen bromide is introduced at the temperature of 150 ℃, the introduction time is 50min, and the XPS analysis is used for analyzing that the mass content of oxygen accounts for 11 percent of the active components.
Example 3 (sample 3)
1% based on the total load (as KNO)3、La(NO3)3Meter, KNO3/La(NO3)31/1) weighing KNO3、La(NO3)3Adding anhydrous ethanol to the powder to prepare an impregnation solution, and adding a certain amount of activated carbon carrier (the carrier has the micropore number of 700-750 m) after all the metal salts are completely dissolved2Per gram, the specific surface area is more than 1000m2/g), and standing and soaking are carried out for 12 hours. Filtering the impregnated catalyst, drying at 150 ℃ for 12h, and roasting at 500 ℃ for 12 h;
385ml of the calcined catalyst precursor is placed in a reaction tube, 50ml/min of hydrogen bromide is introduced at the temperature of 150 ℃, the introduction time is 40min, and the XPS analysis is used for analyzing that the mass content of oxygen accounts for 9.6 percent of the active component.
Example 4 (sample 4)
1% by total loading (as NaNO)3、La(NO3)3Meter. NaNO3/La(NO3)31/1) weighing NaNO3、La(NO3)3Adding anhydrous ethanol to the powder to prepare an impregnation solution, and adding a certain amount of activated carbon carrier (the carrier has the micropore number of 700-750 m) after all the metal salts are completely dissolved2Per g, specific surface area greater than 1000m2And/g) standing and soaking for 12 h. Filtering the impregnated catalyst, drying at 150 ℃ for 12h, and roasting at 400 ℃ for 12 h;
385ml of the roasted catalyst precursor is placed in a reaction tube, 50ml/min of hydrogen bromide is introduced at the temperature of 150 ℃, the introduction time is 55min, and the XPS analysis is utilized to analyze that the mass content of oxygen accounts for 7.5 percent of the active component.
Example 5 (sample 5)
In a total loading of 20% (as KNO)3、NaNO3Meter, KNO3/NaNO31/1) weighing KNO3And NaNO3Adding anhydrous ethanol to the powder to prepare an impregnation solution, and adding a certain amount of coconut shell activated carbon (the number of micropores of the carrier is 700-2Per g, specific surface area greater than 1000m2And/g) standing and soaking for 12 h. Filtering the impregnated catalyst, drying at 80 ℃ for 12h, and roasting at 500 ℃ for 12 h;
385ml of the calcined catalyst precursor is placed in a reaction tube, 50ml/min of hydrogen bromide is introduced at the temperature of 150 ℃, the introduction time is 40min, and the XPS analysis is used for analyzing that the mass content of oxygen accounts for 10.3 percent of the active component.
Example 6 (sample 6)
In a total loading of 20% (as KNO)3、NaNO3And La (NO)3)3Meter, KNO3/NaNO3/La(NO3)31/1/2) weighing KNO3、NaNO3And La (NO)3)3Adding anhydrous ethanol to the powder to prepare an impregnation solution, and adding a certain amount of coconut shell activated carbon (the number of micropores of the carrier is 700-2Per g, specific surface area greater than 1000m2And/g) standing and soaking for 12 h. Filtering the impregnated catalyst, drying at 80 ℃ for 12h, and roasting at 500 ℃ for 12 h;
385ml of the calcined catalyst precursor is placed in a reaction tube, 50ml/min of hydrogen bromide is introduced at the temperature of 150 ℃, the introduction time is 40min, and the XPS analysis is used for analyzing that the mass content of oxygen accounts for 8.5 percent of the active component.
Example 7 (ammonification reaction)
A304 stainless steel reactor was charged with 385ml of catalyst. The reaction pressure is 0.1-0.15 MPa, the reaction temperature is 160 ℃, and the molar ratio of 2, 2-difluoro-1-chloroethane to ammonia gas is 1: the total space velocity of 8, 2, 2-difluoro-1-chloroethane and ammonia gas is 50h-1Freezing and collecting reaction products, wherein the temperature of a tower kettle of a freezing degassing tower is 0 ℃, excessive ammonia enters an ammonia gas storage air bag at the top of the degassing tower, the excessive ammonia enters a reaction system through a booster pump and a flowmeter, the excessive ammonia is returned to the reaction system through a booster pump, materials at the bottom of the freezing degassing tower are pumped into a secondary degassing tower through a metering pump, the temperature of the secondary degassing tower is 30 ℃, unreacted 2, 2-difluoro-1-chloroethane is collected into a 2, 2-difluoro-1-chloroethane collecting tank at the top of the secondary degassing tower, the unreacted 2, 2-difluoro-1-chloroethane is returned to the reaction system through the metering pump, and simultaneously 2, 2-difluoro-1-chloroethane and ammonia are respectively supplemented into a raw material tank, so that the molar ratio of circulating materials 2, 2-difluoro-1-chloroethane, ammonia and newly supplemented 2, 2-difluoro-1-chloroethane to ammonia is 1: the total space velocity of 8, 2, 2-difluoro-1-chloroethane and ammonia gas is 50h-1So as to realize circulation, the material in the tower kettle of the secondary degassing tower is pressed into a crude product groove of the 2, 2-difluoroethylamine, and then is pumped into a rectifying tower by a metering pump, and the temperature of the tower kettle of the rectifying tower is controlledCollecting the finished product of the 2, 2-difluoroethylamine with the purity of more than 99 percent from the tower top at the temperature of 70 ℃. Sampling from the bottom of the freezing degasser tower, carrying out quantitative analysis by GC, and calculating the conversion rate of raw materials and the yield of target products.
TABLE 1 results of GC analysis of ammoniated reaction products of different samples
TABLE 2 conversion, target product selectivity and yield
As can be seen from the data in Table 1, in sample 6, the target 2, 2-difluoroethylamine was present in an amount of up to 58.3% during the amination reaction. The data in table 2 show that the catalyst prepared by the invention is used for the ammonification reaction for synthesizing 2, 2-difluoroethylamine, and the selectivity of the target product is as high as 99.1% and the yield of the target product is 88.2% by using the sample 6 as the catalyst.
Claims (12)
1. A method for preparing an ammoniation catalyst comprising the sequential steps of:
(1) weighing alkali metal salt as a main active component, or weighing alkali metal salt as a main active component and rare earth metal salt as an auxiliary component, adding absolute ethyl alcohol to prepare impregnation liquid, adding a catalyst carrier after dissolution is finished, and standing for impregnation;
(2) filtering, drying and roasting the impregnated catalyst at high temperature;
(3) placing the calcined catalyst precursor in a reaction tube, introducing a certain amount of hydrogen bromide, and reacting at the temperature of 150-;
the alkali metal is sodium and potassium, the rare earth metal is lanthanum, and the catalyst carrier is coconut shell activated carbon.
2. The method according to claim 1, wherein the oxygen element is contained in an amount of 7 to 12% by mass.
3. The preparation method according to claim 1, wherein the loading amount of the active component is 10-30%, and the concentration of the impregnation liquid is 0.1-1 mol/L.
4. The preparation method according to claim 1, wherein the catalyst carrier is coconut shell activated carbon with a pore size of 700-750m2Per g, specific surface area greater than 1000m2/g。
5. The method according to claim 1, wherein the alkali metal salt and the rare earth metal salt are soluble halides, nitrates, sulfates, carbonates, acetates and double salts.
6. The production method according to claim 1, wherein the alkali metal salt is sodium nitrate or potassium nitrate, the rare earth metal salt is lanthanum nitrate, and the mass ratio of the alkali metal salt to the rare earth metal salt is 1: 1.
7. the preparation method as claimed in claim 1, wherein the standing and dipping time is 12-24h, the drying is drying at 80-250 ℃ for 12-36h, and the roasting is roasting at 300-550 ℃ for 12-36 h.
8. The preparation method according to claim 7, wherein the drying is carried out at 80-200 ℃ for 12-24 h; the roasting is carried out at the temperature of 400-500 ℃ for 12-24 h.
9. Ammoniation catalyst obtainable by the process according to any one of claims 1 to 8.
10. Use of an amination catalyst as claimed in claim 9 for the gas-phase continuous amination of 2, 2-difluoro-1-chloroethane to produce 2, 2-difluoroethylamine.
11. Use according to claim 10, the gas phase beingThe conditions for the continuous ammoniation reaction are: the ammoniation catalyst as described in claim 9 is filled in a fixed bed reactor, the reaction pressure is 0.1-0.15 MPa, the reaction temperature is 100 ℃ and 180 ℃, and the molar ratio of 2, 2-difluoro-1-chloroethane to ammonia gas is 1: 6-10; 2, 2-difluoro-1-chloroethane and ammonia gas total space velocity of 10-150h-1。
12. The process according to claim 1, wherein the reaction temperature is 140 ℃ and the molar ratio of 2, 2-difluoro-1-chloroethane to ammonia gas is 1: 8; 2, 2-difluoro-1-chloroethane and ammonia gas total space velocity of 10-50h-1。
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