CN113976128A - Copper-zinc catalyst for preparing N-methylaniline and N, N-dimethylaniline, preparation method and application thereof - Google Patents
Copper-zinc catalyst for preparing N-methylaniline and N, N-dimethylaniline, preparation method and application thereof Download PDFInfo
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- CN113976128A CN113976128A CN202111431091.0A CN202111431091A CN113976128A CN 113976128 A CN113976128 A CN 113976128A CN 202111431091 A CN202111431091 A CN 202111431091A CN 113976128 A CN113976128 A CN 113976128A
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- methylaniline
- zinc
- dimethylaniline
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- 239000003054 catalyst Substances 0.000 title claims abstract description 121
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 title claims abstract description 118
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 title claims abstract description 116
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 75
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000011148 porous material Substances 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 14
- 239000010439 graphite Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 239000010949 copper Substances 0.000 claims abstract description 5
- 239000011701 zinc Substances 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 42
- 239000007788 liquid Substances 0.000 claims description 21
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 230000032683 aging Effects 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 239000005749 Copper compound Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 150000001880 copper compounds Chemical class 0.000 claims description 5
- 150000003752 zinc compounds Chemical class 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- -1 alcohol amine Chemical class 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 7
- 238000007069 methylation reaction Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 43
- 229910052757 nitrogen Inorganic materials 0.000 description 25
- 238000005303 weighing Methods 0.000 description 18
- 238000000967 suction filtration Methods 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 15
- 230000009467 reduction Effects 0.000 description 15
- 238000006722 reduction reaction Methods 0.000 description 15
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 11
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 11
- 239000002244 precipitate Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000975 dye Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- IWDQPCIQCXRBQP-UHFFFAOYSA-M Fenaminosulf Chemical compound [Na+].CN(C)C1=CC=C(N=NS([O-])(=O)=O)C=C1 IWDQPCIQCXRBQP-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
Classifications
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/18—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of catalyst N-methylation, and particularly relates to a copper-zinc catalyst for preparing N-methylaniline and N, N-dimethylaniline, and a preparation method and application thereof. The mol ratio of copper to zinc in the copper-zinc catalyst is 3: 1-1: 4, controlling the specific surface area of the catalyst to be 15-30 m2The pore diameter is 15-25 nm. The copper-zinc catalyst and graphite are pressed and formed together, the mixture is loaded into a fixed bed reactor, catalytic reduction is firstly carried out, and then aniline and methanol are used as raw materials in the fixed bed reactor, and N-methylaniline and/or N, N-dimethylaniline can be obtained by adjusting specific process conditions. The invention solves the problems of the traditional preparation of N-methylaniline andthe method has the advantages of low yield of the N, N-dimethylaniline, simplification and the like, and simultaneously, the method has few raw material types for preparing the catalyst and simple reaction process of the catalyst, so the cost for preparing the N-methylaniline and the N, N-dimethylaniline is greatly reduced.
Description
Technical Field
The invention belongs to the technical field of catalyst N-methylation, and particularly relates to a copper-zinc catalyst for preparing N-methylaniline and N, N-dimethylaniline, and a preparation method and application thereof.
Background
Aniline N-methylation is an industrially important reaction, and N, N-dimethylaniline is an important chemical intermediate, is widely applied to the production and manufacturing industries of dyes, medicines, pesticides, explosives, plastics and the like, and is also a normal-temperature curing accelerator. DMA has large consumption in the fields of dye and spice, wherein dyes such as common azo dyes, basic bright yellow, basic purple and the like, and spices such as vanillin are used for synthesizing fenaminosulf in the aspect of pesticides, and the consumption per year is also large. Meanwhile, N-methylaniline used as a main intermediate in the process of producing N, N-dimethylaniline is also an important chemical intermediate and is applied to a wide range of chemical industries.
The traditional industrial production of N-methylaniline and N, N-dimethylaniline has the defects of strong pollution, complex reaction process, certain danger and single production.
Disclosure of Invention
In order to overcome the problems in the prior art, the application provides a preparation method and application of a copper-zinc catalyst for preparing N-methylaniline and N, N-dimethylaniline.
The method follows the aim of green chemistry, the types of the raw materials for preparing the catalyst are few, the reaction process of the catalyst is simple, the yield is high, the cost for preparing the N-methylaniline and the N, N-dimethylaniline is greatly reduced, and the method has industrial application prospect. In order to realize the purpose, the adopted technical scheme is as follows: a copper zinc catalyst for the preparation of N-methylaniline and N, N-dimethylaniline, wherein the molar ratio of copper to zinc is 3: 1-1: 4, the catalyst can be used for catalyzing two substances of N-methylaniline and N, N-dimethylaniline respectively by changing reaction conditions, and meanwhile, the catalyst prepared by the method has few raw material types and simple reaction process.
Further, the copper-zinc catalyst is prepared by coprecipitation of a zinc compound and a copper compound under the action of a precipitator. When in use, the catalyst is made into a cylindrical shape and is reacted through a fixed bed to obtain N-methylaniline and N, N-dimethylaniline products.
Further, the precipitant is any one of sodium bicarbonate and sodium carbonate. And the alkali with high solubility in water is selected, so that the adsorption of the precipitate on the alkali can be reduced, and the activity of the catalyst is further improved.
Further, the zinc compound is any one or more of zinc nitrate, zinc sulfate and zinc chloride.
Further, the copper compound is any one or more of copper nitrate, copper sulfate or copper chloride.
Furthermore, the specific surface area of the catalyst is controlled to be 15-30 m2The pore diameter is 15-25 nm. The specific surface area and the pore diameter are too small, which is beneficial to the conversion rate of aniline and the selectivity of N-methylaniline; the specific surface area and the pore diameter are too large, so that the selectivity of the N, N-dimethylaniline is improved.
Further, the specific preparation method of the catalyst comprises the following operation steps:
s1, stirring and reacting a precipitant aqueous solution with the mass concentration of 5-20% with a zinc compound and a copper compound at the temperature of 60-90 ℃ (the stirring speed is further preferably 100-400 r/min);
s2, when the reaction is finished, the pH value of a reaction system is 7-10, aging is carried out for 1-24 hours at the temperature of 20-90 ℃, and then filtering and washing are carried out;
and S3, drying at 80-100 ℃ to remove water, roasting at 300-500 ℃ (preferably 400 ℃), and tabletting for molding (preferably 4h for roasting). If the calcination temperature is too high, the pore diameter is large, the by-products generated are increased, and polymerization may occur, and if the calcination temperature is too low, the pore diameter of the catalyst may be too small, which may not catalyze the reaction.
Further, the number of washing in step S2 is 2 to 8. The content of sodium oxide can be controlled by the washing times of the catalyst by the deionized water, and further the optimal activity of the catalyst is obtained. The specific operation is that when aging, the supernatant is sucked out and then added with deionized water continuously for stirring, and then aging is carried out again and repeated for a plurality of times.
The specific surface area is controlled to be 15-30 m through the roasting temperature of a muffle furnace and the dropping speed in the coprecipitation reaction2The pore diameter is 15-25 nm, which is beneficial to the reaction.
The copper-zinc catalyst is used for preparing N-methylaniline or N, N-dimethylaniline, and comprises the following steps: the preparation method comprises the steps of co-pressing and forming a copper-zinc catalyst and graphite (generally in a cylindrical shape) which is used as a binder, is beneficial to demolding and does not participate in reaction), putting the mixture into a fixed bed reactor, carrying out catalytic reduction, taking aniline and methanol as raw materials in the fixed bed reactor, and carrying out liquid-air velocity for 0.1-0.5 h at the temperature of 240-270 ℃ in a certain range-1Reacting under the conditions that the pressure is 0-2 MPa and the ratio of aniline to methanol is 1: 2-1: 7 to obtain a product.
Further, the pressure is 1.5-2 MPa, and the molar ratio of copper to zinc in the copper-zinc catalyst is 1: and 3, the molar ratio of the alcohol amine is 1: 5-1: 7, and the yield of the N, N-dimethylaniline can be improved by optimizing the step.
Furthermore, when the pressure can be controlled at about normal pressure, the yield of N-methylaniline can be improved.
In conclusion, the invention has the following beneficial effects:
the preparation process of the catalyst of the invention follows the aim of green chemistry, and the two products of N-methylaniline and N, N-dimethylaniline are respectively prepared by catalysis through changing reaction conditions. The method solves the problems of low yield, simplification (the same catalyst can realize the efficient preparation of two products of the N-methylaniline and the N, N-dimethylaniline) and the like in the traditional process for preparing the N-methylaniline and the N, N-dimethylaniline, and simultaneously, the method for preparing the catalyst has the advantages of few raw material types and simple catalyst reaction process, so the cost for preparing the N-methylaniline and the N, N-dimethylaniline is greatly reduced.
Detailed Description
In order to further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the specific embodiments, features and effects of the catalyst for preparing N-methylaniline and N, N-dimethylaniline and the method for preparing N-methylaniline and N, N-dimethylaniline according to the present invention are described in detail. However, the present invention is not limited to the following embodiments, and those skilled in the art can implement the present invention in other embodiments according to the disclosure of the present invention, or make simple changes or modifications to the design structure and idea of the present invention, and fall into the protection scope of the present invention. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
Example 1: catalyst for preparing N-methylaniline and N, N-dimethylaniline and method for preparing N-methylaniline and N, N-dimethylaniline
(1) The preparation method of the copper-zinc catalyst comprises the following steps:
s1, weighing 53g of sodium carbonate, dissolving the sodium carbonate in 530g of water, and stirring at 70 ℃ at 300 r/min;
s2, weighing 74.4g of zinc nitrate hexahydrate and 60.4g of copper nitrate trihydrate, dissolving the zinc nitrate hexahydrate and the copper nitrate trihydrate in 200g of water, dropwise adding the mixture into a sodium carbonate solution through a constant-pressure dropping funnel, keeping the pH value to be 7.5 after the dropwise adding is completed, continuously reacting for 1h, ageing for 2h under natural cooling, washing for 2 times, and performing suction filtration;
s3, drying the precipitate after suction filtration at 90 ℃ for 8h, and roasting at 400 ℃ for 4 h. The specific surface area of the catalyst, characterized by BET, is 17.1m2G, pore diameter of 16.6 nm.
(2) The method for preparing N-methylaniline and N, N-dimethylaniline by using the copper-zinc catalyst comprises the following steps:
0.5g of graphite is weighed and evenly mixed with the roasted catalyst, and then pressed into the catalyst
The cylindrical catalyst of (1).
20mL of the above cylindrical catalyst was charged in a fixed bed reactor, and 5% H was introduced at normal temperature and pressure2-95％N2Setting the temperature of the fixed bed to be 160 ℃ after 3h, maintaining the temperature for 2h, and continuously heating to 230 ℃ after 3hAnd maintaining for 2h to complete the catalyst reduction.
After reduction, at 250 ℃ and normal pressure, n (aniline): n (methanol): 1:5, liquid space velocity is 0.2h-1And the nitrogen flow rate is 80 ml/min. See the text end table for specific data.
At 270 deg.C, 1.5MPa, n (aniline): n (methanol): 1:5, liquid space velocity 0.3h-1And the nitrogen flow rate is 80 ml/min. See the text end table for specific data.
Example 2: catalyst for preparing N-methylaniline and N, N-dimethylaniline and method for preparing N-methylaniline and N, N-dimethylaniline
(1) The preparation method of the copper-zinc catalyst comprises the following steps:
s1, weighing 53g of sodium carbonate, dissolving the sodium carbonate in 530g of water, and stirring at 70 ℃ at 300 r/min;
s2, weighing 99.2g of zinc nitrate hexahydrate and 40.3g of copper nitrate trihydrate, dissolving the zinc nitrate hexahydrate and the copper nitrate trihydrate in 200g of water, dropwise adding the mixture into a sodium carbonate solution through a constant-pressure dropping funnel, keeping the pH value to be 7.5 after the dropwise adding is completed, continuously reacting for 1h, ageing for 2h under natural cooling, washing for 2 times, and performing suction filtration;
s3, drying the precipitate after suction filtration at 90 ℃ for 8h, and roasting at 400 ℃ for 4 h. The specific surface area of the catalyst, characterized by BET, is 21.8m2G, pore diameter of 19.7 nm.
(2) The method for preparing N-methylaniline and N, N-dimethylaniline by using the copper-zinc catalyst comprises the following steps:
0.5g of graphite is weighed and evenly mixed with the roasted catalyst, and then pressed into the catalyst
The cylindrical catalyst of (1).
20mL of the above cylindrical catalyst was charged in a fixed bed reactor, and 5% H was introduced at normal temperature and pressure2-95％N2And (3) setting the temperature of the hydrogen-nitrogen mixed gas in the fixed bed to be 3 hours, heating to 160 ℃, maintaining for 2 hours, continuously heating for 3 hours to 230 ℃, and maintaining for 2 hours to complete the reduction of the catalyst.
After reduction, at 250 ℃ and normal pressure, n (aniline): n (methanol): 1:5, liquid space velocity is 0.2h-1And the nitrogen flow rate is 80 ml/min. See the text end table for specific data.
At 270 deg.C, 1.5MPa, n (aniline): n (methanol): 1:5, liquid space velocity 0.3h-1And the nitrogen flow rate is 80 ml/min. See the text end table for specific data.
Example 3: catalyst for preparing N-methylaniline and N, N-dimethylaniline and method for preparing N-methylaniline and N, N-dimethylaniline
(1) The preparation method of the copper-zinc catalyst comprises the following steps:
s1, weighing 127.2g of sodium carbonate, dissolving in 1272g of water, and stirring at 70 ℃ at 300 r/min;
s2, weighing 119g of zinc nitrate hexahydrate and 193.2g of copper nitrate trihydrate, dissolving in 500g of water, dropwise adding into a sodium carbonate solution through a constant-pressure dropping funnel, keeping the pH value to be 7.5 after complete dropwise adding, continuing to react for 1h, naturally cooling, aging for 2h, washing for 2 times, and performing suction filtration;
s3, drying the precipitate after suction filtration at 90 ℃ for 8h, and roasting at 400 ℃ for 4 h. The specific surface area of the catalyst, characterized by BET, is 17.2m2G, pore diameter of 17.2 nm.
(2) The method for preparing N-methylaniline and N, N-dimethylaniline by using the copper-zinc catalyst comprises the following steps:
weighing 1.0g of graphite, uniformly mixing the graphite with the roasted catalyst, and pressing the mixture into the catalyst
The cylindrical catalyst of (1).
20mL of the above cylindrical catalyst was charged in a fixed bed reactor, and 5% H was introduced at normal temperature and pressure2-95％N2And (3) setting the temperature of the hydrogen-nitrogen mixed gas in the fixed bed to be 3 hours, heating to 160 ℃, maintaining for 2 hours, continuously heating for 3 hours to 230 ℃, and maintaining for 2 hours to complete the reduction of the catalyst.
After reduction, at 250 ℃ and normal pressure, n (aniline): n (methanol): 1:5, liquid space velocity is 0.2h-1And the nitrogen flow rate is 80 ml/min. See the text end table for specific data.
At 250 deg.C and normal pressure, n (aniline): n (methanol) ═ 1:2, liquid space velocity 0.2h-1And the nitrogen flow rate is 80 ml/min. See the text end table for specific data.
At the temperature of 270 c,1.5MPa, n (aniline): n (methanol) ═ 1:5, liquid space velocity 0.3h-1And the nitrogen flow rate is 80 ml/min. See the text end table for specific data.
Example 4: catalyst for preparing N-methylaniline and N, N-dimethylaniline and method for preparing N-methylaniline and N, N-dimethylaniline
(1) The preparation method of the copper-zinc catalyst comprises the following steps:
s1, weighing 84.8g of sodium carbonate, dissolving in 848g of water, and stirring at 70 ℃ at 300 r/min;
s2, weighing 59.5g of zinc nitrate hexahydrate and 144.9g of copper nitrate trihydrate, dissolving in 320g of water, dropwise adding into a sodium carbonate solution through a constant-pressure dropping funnel, keeping the pH value to be 7.5 after complete dropwise adding, continuously reacting for 1h, ageing for 2h under natural cooling, washing for 2 times, and performing suction filtration;
s3, drying the precipitate after suction filtration at 90 ℃ for 8h, and roasting at 400 ℃ for 4 h. The specific surface area of the catalyst, characterized by BET, is 16.9m2G, pore diameter of 14.2 nm.
(2) The method for preparing N-methylaniline and N, N-dimethylaniline by using the copper-zinc catalyst comprises the following steps:
0.5g of graphite is weighed and evenly mixed with the roasted catalyst, and then pressed into the catalyst
The cylindrical catalyst of (1).
20mL of the above cylindrical catalyst was charged in a fixed bed reactor, and 5% H was introduced at normal temperature and pressure2-95％N2And (3) setting the temperature of the hydrogen-nitrogen mixed gas in the fixed bed to be 3 hours, heating to 160 ℃, maintaining for 2 hours, continuously heating for 3 hours to 230 ℃, and maintaining for 2 hours to complete the reduction of the catalyst.
After reduction, at 250 ℃ and normal pressure, n (aniline): n (methanol): 1:5, liquid space velocity is 0.2h-1And the nitrogen flow rate is 80 ml/min. See the text end table for specific data.
At 270 deg.C, 1.5MPa, n (aniline): n (methanol): 1:5, liquid space velocity 0.3h-1And the nitrogen flow rate is 80 ml/min. See the text end table for specific data.
Example 5: catalyst for preparing N-methylaniline and N, N-dimethylaniline and method for preparing N-methylaniline and N, N-dimethylaniline
(1) The preparation method of the copper-zinc catalyst comprises the following steps:
s1, weighing 84.8g of sodium carbonate, dissolving in 848g of water, and stirring at 70 ℃ at 300 r/min;
s2, weighing 178.5g of zinc nitrate hexahydrate and 48.3g of copper nitrate trihydrate, dissolving in 320g of water, dropwise adding into a sodium carbonate solution through a constant-pressure dropping funnel, keeping the pH value at 7.5 after complete dropwise adding, continuously reacting for 1h, aging for 2h under natural cooling, washing for 2 times, and performing suction filtration;
s3, drying the precipitate after suction filtration at 90 ℃ for 8h, and roasting at 400 ℃ for 4 h. The specific surface area of the catalyst, characterized by BET, is 23.7m2G, pore diameter of 21.4 nm.
(2) The method for preparing N-methylaniline and N, N-dimethylaniline by using the copper-zinc catalyst comprises the following steps:
0.5g of graphite is weighed and evenly mixed with the roasted catalyst, and then pressed into the catalyst
The cylindrical catalyst of (1).
20mL of the above cylindrical catalyst was charged in a fixed bed reactor, and 5% H was introduced at normal temperature and pressure2-95％N2And (3) setting the temperature of the hydrogen-nitrogen mixed gas in the fixed bed to be 3 hours, heating to 160 ℃, maintaining for 2 hours, continuously heating for 3 hours to 230 ℃, and maintaining for 2 hours to complete the reduction of the catalyst.
After reduction, at 250 ℃ and normal pressure, n (aniline): n (methanol): 1:5, liquid space velocity is 0.2h-1And the nitrogen flow rate is 80 ml/min. See the text end table for specific data.
At 270 deg.C, 1.5MPa, n (aniline): n (methanol): 1:5, liquid space velocity 0.3h-1And the nitrogen flow rate is 80 ml/min. See the text end table for specific data.
At 270 deg.C, 1.5MPa, n (aniline): n (methanol): 1:7, liquid space velocity 0.3h-1And the nitrogen flow rate is 80 ml/min. See the text end table for specific data.
Example 6: catalyst for preparing N-methylaniline and N, N-dimethylaniline and method for preparing N-methylaniline and N, N-dimethylaniline
(1) The preparation method of the copper-zinc catalyst comprises the following steps:
s1, weighing 84.8g of sodium carbonate, dissolving in 848g of water, and stirring at 70 ℃ at 300 r/min;
s2, weighing 190.4g of zinc nitrate hexahydrate and 38.7g of copper nitrate trihydrate, dissolving the zinc nitrate hexahydrate and the copper nitrate trihydrate in 320g of water, dropwise adding the mixture into a sodium carbonate solution through a constant-pressure dropping funnel, keeping the pH value to be 7.5 after the dropwise adding is completed, continuously reacting for 1h, ageing for 2h under natural cooling, washing for 2 times, and performing suction filtration;
s3, drying the precipitate after suction filtration at 90 ℃ for 8h, and roasting at 400 ℃ for 4 h. The specific surface area of the catalyst, characterized by BET, is 26.1m2G, pore diameter of 22.4 nm.
(2) The method for preparing N-methylaniline and N, N-dimethylaniline by using the copper-zinc catalyst comprises the following steps:
0.5g of graphite is weighed and evenly mixed with the roasted catalyst, and then pressed into the catalyst
The cylindrical catalyst of (1).
20mL of the above cylindrical catalyst was charged in a fixed bed reactor, and 5% H was introduced at normal temperature and pressure2-95％N2And (3) setting the temperature of the hydrogen-nitrogen mixed gas in the fixed bed to be 3 hours, heating to 160 ℃, maintaining for 2 hours, continuously heating for 3 hours to 230 ℃, and maintaining for 2 hours to complete the reduction of the catalyst.
After reduction, at 250 ℃ and normal pressure, n (aniline): n (methanol): 1:5, liquid space velocity is 0.2h-1And the nitrogen flow rate is 80 ml/min. See the text end table for specific data.
At 270 deg.C, 1.5MPa, n (aniline): n (methanol): 1:5, liquid space velocity 0.3h-1And the nitrogen flow rate is 80 ml/min. See the text end table for specific data.
Example 7: catalyst for preparing N-methylaniline and N, N-dimethylaniline and method for preparing N-methylaniline and N, N-dimethylaniline
(1) The preparation method of the copper-zinc catalyst comprises the following steps:
s1, weighing 127.5g of sodium carbonate, dissolving in 1275g of water, and stirring at 70 ℃ at 300 r/min;
s2, weighing 119g of zinc nitrate hexahydrate and 193.2g of copper nitrate trihydrate, dissolving in 500g of water, dropwise adding into a sodium carbonate solution through a constant-pressure dropping funnel, keeping the pH value to be 7.5 after complete dropwise adding, continuing to react for 1h, naturally cooling, aging for 2h, washing for 4 times, and performing suction filtration;
s3, drying the precipitate after suction filtration at 90 ℃ for 8h, and roasting at 400 ℃ for 4 h. The specific surface area of the catalyst, characterized by BET, is 17.3m2G, pore diameter of 17.3 nm.
(2) The method for preparing N-methylaniline and N, N-dimethylaniline by using the copper-zinc catalyst comprises the following steps:
weighing 1.0g of graphite, uniformly mixing the graphite with the roasted catalyst, and pressing the mixture into the catalyst
The cylindrical catalyst of (1).
20mL of the above cylindrical catalyst was charged in a fixed bed reactor, and 5% H was introduced at normal temperature and pressure2-95％N2And (3) setting the temperature of the hydrogen-nitrogen mixed gas in the fixed bed to be 3 hours, heating to 160 ℃, maintaining for 2 hours, continuously heating for 3 hours to 230 ℃, and maintaining for 2 hours to complete the reduction of the catalyst.
At 250 deg.C and normal pressure, n (aniline): n (methanol) ═ 1:2, liquid space velocity 0.2h-1And the nitrogen flow rate is 80 ml/min. See the text end table for specific data.
At 270 deg.C, 1.5MPa, n (aniline): n (methanol): 1:5, liquid space velocity 0.3h-1And the nitrogen flow rate is 80 ml/min. See the text end table for specific data.
Example 8: catalyst for preparing N-methylaniline and N, N-dimethylaniline and method for preparing N-methylaniline and N, N-dimethylaniline
(1) The preparation method of the copper-zinc catalyst comprises the following steps:
s1, firstly weighing 85g of sodium carbonate, dissolving the sodium carbonate in 850g of water, and stirring at 70 ℃ at 300 r/min;
s2, weighing 178.7g of zinc nitrate hexahydrate and 48.4g of copper nitrate trihydrate, dissolving in 320g of water, dropwise adding into a sodium carbonate solution through a constant-pressure dropping funnel, keeping the pH value at 7.5 after complete dropwise adding, continuously reacting for 1h, ageing for 2h under natural cooling, washing for 6 times, and performing suction filtration;
s3, drying the precipitate after suction filtration at 90 ℃ for 8h, and roasting at 400 ℃ for 4 h. The specific surface area of the catalyst, characterized by BET, is 23.6m2G, pore diameter of 21.5 nm.
(2) The method for preparing N-methylaniline and N, N-dimethylaniline by using the copper-zinc catalyst comprises the following steps:
0.5g of graphite is weighed and evenly mixed with the roasted catalyst, and then pressed into the catalyst
The cylindrical catalyst of (1).
20mL of the above cylindrical catalyst was charged in a fixed bed reactor, and 5% H was introduced at normal temperature and pressure2-95％N2And (3) setting the temperature of the hydrogen-nitrogen mixed gas in the fixed bed to be 3 hours, heating to 160 ℃, maintaining for 2 hours, continuously heating for 3 hours to 230 ℃, and maintaining for 2 hours to complete the reduction of the catalyst.
After reduction, at 250 ℃ and normal pressure, n (aniline): n (methanol): 1:5, liquid space velocity is 0.2h-1And the nitrogen flow rate is 80 ml/min. See the text end table for specific data.
At 270 deg.C, 1.5MPa, n (aniline): n (methanol): 1:7, liquid space velocity 0.3h-1And the nitrogen flow rate is 80 ml/min. See the text end table for specific data.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A copper-zinc catalyst for the preparation of N-methylaniline and N, N-dimethylaniline, characterized in that: the mol ratio of copper to zinc in the catalyst is 3: 1-1: 4, controlling the specific surface area of the catalyst to be 15-30 m2The pore diameter is 15-25 nm.
2. The method for preparing a copper-zinc catalyst for the preparation of N-methylaniline and N, N-dimethylaniline according to claim 1, wherein: the method comprises the following steps:
s1, stirring and reacting a precipitant aqueous solution with the mass concentration of 5-20% with a zinc compound and a copper compound at 60-90 ℃;
s2, when the reaction is finished, the pH value of a reaction system is 7-10, and then the reaction system is aged for 1-24 hours at the temperature of 20-90 ℃ and then filtered and washed;
and S3, drying at 80-100 ℃, removing water, roasting at 300-500 ℃, tabletting and forming (the roasting time is preferably 4 hours). If the calcination temperature is too high, the pore diameter is large, the by-products generated are increased, and polymerization may occur, and if the calcination temperature is too low, the pore diameter of the catalyst may be too small, which may not catalyze the reaction.
3. The method for preparing a copper-zinc catalyst for the preparation of N-methylaniline and N, N-dimethylaniline according to claim 2, characterized in that: in step S1, the precipitant is either sodium bicarbonate or sodium carbonate.
4. The method for preparing a copper-zinc catalyst for the preparation of N-methylaniline and N, N-dimethylaniline according to claim 2, characterized in that: the zinc compound in step S1 is any one or more of zinc nitrate, zinc sulfate, and zinc chloride.
5. The method for preparing a copper-zinc catalyst for the preparation of N-methylaniline and N, N-dimethylaniline according to claim 2, characterized in that: the copper compound in step S1 is any one or more of copper nitrate, copper sulfate, or copper chloride.
6. The method for preparing a copper-zinc catalyst for the preparation of N-methylaniline and N, N-dimethylaniline according to claim 2, characterized in that: in the step S2, the washing times are 2-8 times, and the method is to replace the liquid in the aging period for many times.
7. The method for preparing a copper-zinc catalyst for the preparation of N-methylaniline and N, N-dimethylaniline according to claim 2, characterized in that: the calcination temperature in step S3 was 400 ℃.
8. Use of a copper-zinc catalyst for the preparation of N-methylaniline and N, N-dimethylaniline according to claim 1, characterized in that: the method comprises the following steps: pressing and forming a copper-zinc catalyst and graphite together, putting the copper-zinc catalyst and the graphite into a fixed bed reactor, firstly carrying out catalytic reduction, and then taking aniline and methanol as raw materials in the fixed bed reactor at the temperature of 240-270 ℃ and the liquid-air speed of 0.1-0.5 h-1Reacting under the conditions that the pressure is 0-2 MPa and the ratio of aniline to methanol is 1: 2-1: 7 to obtain N-methylaniline and/or N, N-dimethylaniline.
9. Use of the copper-zinc catalyst for the preparation of N-methylaniline and N, N-dimethylaniline according to claim 8, characterized in that: the pressure is 1.5-2 MPa, and the molar ratio of copper to zinc in the copper-zinc catalyst is 1: 3, the molar ratio of the alcohol amine is 1: 5-1: 7;
alternatively, the pressure is controlled to be normal pressure.
10. Use of the copper-zinc catalyst for the preparation of N-methylaniline and N, N-dimethylaniline according to claim 8, characterized in that: the reaction temperature is controlled to be 250 ℃ and the liquid air speed is controlled to be 0.2h-1At normal pressure, the molar ratio of aniline to methanol is 1: 2;
or, controlling the reaction temperature at 270 ℃ and the liquid air speed for 0.3h-1The pressure is 1.5MPa, and the molar ratio of aniline to methanol is 1: 7.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU95110305A (en) * | 1995-06-21 | 1996-05-27 | М.И. Якушкин | Method for production of n-methyl aniline |
| CN103028411A (en) * | 2013-01-07 | 2013-04-10 | 南京尊龙化工有限公司 | Novel N-methyl aniline catalyst synthesized through chromium-free gas phase method |
| CN104276957A (en) * | 2013-07-09 | 2015-01-14 | 中国科学院兰州化学物理研究所 | Method for preparing N-methyl or N,N-dimethyl amine compound |
-
2021
- 2021-11-29 CN CN202111431091.0A patent/CN113976128B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU95110305A (en) * | 1995-06-21 | 1996-05-27 | М.И. Якушкин | Method for production of n-methyl aniline |
| CN103028411A (en) * | 2013-01-07 | 2013-04-10 | 南京尊龙化工有限公司 | Novel N-methyl aniline catalyst synthesized through chromium-free gas phase method |
| CN104276957A (en) * | 2013-07-09 | 2015-01-14 | 中国科学院兰州化学物理研究所 | Method for preparing N-methyl or N,N-dimethyl amine compound |
Non-Patent Citations (2)
| Title |
|---|
| 张延荣等: "《环境科学与工程实验室安全与操作规范》", 31 January 2021, 华中科技大学出版社, pages: 16 * |
| 胡云峰等: "共沉淀法制备Cu/ZnO催化剂用于1, 4-丁二醇合成吡咯", 《化工进展》, vol. 33, no. 4, pages 941 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116159602A (en) * | 2023-03-01 | 2023-05-26 | 江苏京盈化工新材料有限公司 | Reduction process of copper catalyst for N-methylaniline synthesis |
| CN116159602B (en) * | 2023-03-01 | 2023-09-15 | 西南化工研究设计院有限公司 | Reduction process of copper catalyst for N-methylaniline synthesis |
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