CN107115881A - A kind of preparation method and application of the catalyst synthesized for N methylanilines - Google Patents
A kind of preparation method and application of the catalyst synthesized for N methylanilines Download PDFInfo
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- CN107115881A CN107115881A CN201710299685.8A CN201710299685A CN107115881A CN 107115881 A CN107115881 A CN 107115881A CN 201710299685 A CN201710299685 A CN 201710299685A CN 107115881 A CN107115881 A CN 107115881A
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- Prior art keywords
- methylphenylamine
- catalyst
- preparation
- nitrate
- aluminium
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- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical class CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 40
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 239000007864 aqueous solution Substances 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 28
- 239000002244 precipitate Substances 0.000 claims description 22
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 20
- 239000004411 aluminium Substances 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 19
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 229910001593 boehmite Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000012065 filter cake Substances 0.000 claims description 12
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000000748 compression moulding Methods 0.000 claims description 11
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 10
- 206010013786 Dry skin Diseases 0.000 claims description 10
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- 239000007788 liquid Substances 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 159000000013 aluminium salts Chemical class 0.000 claims description 4
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910052596 spinel Inorganic materials 0.000 claims description 4
- 239000011029 spinel Substances 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 230000029087 digestion Effects 0.000 claims description 2
- 239000012808 vapor phase Substances 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 9
- 229910002651 NO3 Inorganic materials 0.000 description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 8
- 238000000975 co-precipitation Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 230000001376 precipitating effect Effects 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
Classifications
-
- 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
- B01J23/005—Spinels
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/868—Chromium copper and chromium
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to chemical technology field, and in particular to a kind of preparation method and application of the catalyst synthesized for N methylanilines.Catalyst uses copper zinc chrome aluminate catalyst, and the catalyst need not carry out hydrogenating reduction pretreatment before the use, and the selectivity that the conversion per pass of aniline is up to more than 90%, N methylanilines is up to more than 98%.
Description
Technical field
The invention belongs to chemical technology field, and in particular to a kind of preparation side of the catalyst synthesized for methylphenylamine
Method and application.
Background technology
Methylphenylamine has the outstanding capability of antidetonance, is a kind of important intermediate, is widely used in medicine, agricultural chemicals
With the field such as dyestuff.The method of synthesis methylphenylamine is broadly divided into liquid phase synthesizing method and gas phase synthesis method.Liquid phase synthesizing method by
In having used strong acid as catalyst, so as to cause the environmental pollution of consersion unit burn into and excessively accessory substance of unfavorable separation etc.
The problems such as, so little by little being replaced by gas phase synthesis method.
Gas phase synthesis method uses environmentally friendly solid catalyst, with CH3OH is anti-in fixed bed as alkylating reagent
Catalysed aniline under gas phase condition is answered in device to synthesize methylphenylamine., should at present using more for Cu oxide mixed catalyst
Although class solid catalyst is with higher catalytic activity, catalyst must in advance be located by hydrogenating reduction before the use
Reason, the purpose is to the cupric oxide of catalytically inactive in catalyst system is reduced into the elemental copper with catalytic activity.But add
Hydrogen reduction pretreatment has certain danger and inconvenience, is not convenient to use to a certain extent.It is therefore desirable to develop one
Plant the synthesis technique of new methylphenylamine.
The content of the invention
The present invention is in order to avoid in methylphenylamine synthesis technique, catalyst needs the hydrogenation by inconvenience before the use
There is provided a kind of preparation method of the catalyst synthesized for methylphenylamine for the link of reduction pretreatment：
(1) mantoquita, zinc salt, chromic salts, aluminium salt are made into mixed liquor, the mixed liquor are adjusted to alkalescence and is aged,
Wherein, mantoquita, zinc salt, chromic salts, aluminium salt are according to copper nitrate, zinc nitrate, chromic nitrate, aluminum nitrate 1~3：1~3：1：3
Mixed in molar ratio, mixing temperature be 60 DEG C,
The pH value of regulation mixed liquor specific sodium hydrate aqueous solution regulation mixed liquor for use 0.1mol/L when being alkalescence for
10,
Digestion time is 10 hours；
(2) by the system centrifugal treating after being aged in step (1), by the Washing of Filter Cake of gained and drying, copper zinc chrome is obtained
Aluminium quaternary co-precipitate,
It is 7 and in the lower 80 DEG C of dryings of normal pressure 10 hours by the Washing of Filter Cake of gained to pH value；
(3) it is the copper zinc chrome with spinel structure by the copper zinc chrome aluminium quaternary co-precipitate calcination obtained in step (2)
Aluminium four-way catalyst,
Co-precipitate calcination 6 hours at 900~1000 DEG C；
(4) it is the copper zinc chrome aluminium four-way catalyst of gained in step (3) and aluminum oxide, boehmite and salpeter solution is mixed
Uniform rear compression molding is closed, obtaining sheet has the copper zinc chrome aluminium four-way catalyst of spinel structure, the solute matter of salpeter solution
Amount fraction is 15wt%, and copper zinc chrome aluminium four-way catalyst, aluminum oxide, boehmite, salpeter solution press 30：10：1：5 quality
Than well mixed.
Present invention also offers a kind of application of above-mentioned catalyst in vapor phase method synthesizes methylphenylamine technique, this is urged
Agent is placed in fixed bed reactors, in normal pressure, 245~265 DEG C of reaction temperature, 0.1~0.3h of liquid air speed-1, aniline and first
Alcohol mol ratio 1：Reaction synthesis methylphenylamine under conditions of 2~4.
The beneficial effects of the present invention are：The catalyst used in synthesis technique of the present invention is that possess copper zinc chrome aluminate
The composite oxides of structure, due to the synergy of each component in spinel structure so that copper zinc chrome aluminate combined oxidation
Thing possesses catalytic activity, it is to avoid the step of catalyst is pre-processed by hydrogenating reduction, and this catalyst be likewise supplied with it is outstanding
Catalytic performance.
Brief description of the drawings
Fig. 1 is the mass spectrogram of the methylphenylamine catalyzed and synthesized in embodiment 3.
Embodiment
Embodiment 1
(1) accurate copper nitrate aqueous solution 87.5mL (0.00875mol), the 0.1mol/L zinc nitrate for measuring 0.1mol/L
Aqueous solution 262.5mL (0.02625mol), 0.1mol/L chromic nitrate 175mL (0.0175mol) and 0.1mol/L aluminum nitrate
525mL (0.0525mol) is sufficiently mixed, and is taken 0.1mol/L sodium hydrate aqueous solution as precipitating reagent, is allowed using coprecipitation
Nitrate mixed solution and sodium hydrate aqueous solution react in 60 DEG C of water-baths reach 10 to pH after, be aged 10 hours；
(2) it is 7 and in normal pressure by the Washing of Filter Cake of gained to pH value by the system centrifugal treating after being aged in step (1)
Lower 80 DEG C of dryings 10 hours, obtain copper zinc chrome aluminium quaternary co-precipitate；
(3) co-precipitate obtained in step (2) is placed on 900 DEG C of Muffle kiln roasting 6h, natural cooling；
(4) salpeter solution of the mixture of gained in step (3) and aluminum oxide, boehmite, 15wt% is pressed 30：
10：1：After 5 mass ratio is well mixed, press compression molding is utilized.
The preformed catalyst prepared in 60g the present embodiment is added in fixed bed reactors, is 245 in reaction temperature
DEG C, liquid air speed 0.1h-1, methanol and aniline mol ratio be 2:Methylphenylamine is synthesized under conditions of 1.
The aniline conversion of one way is 23.49%, and methylphenylamine is selectively 100%.
Embodiment 2
(1) accurate copper nitrate aqueous solution 116.7mL (0.01167mol), the 0.1mol/L zinc nitrate for measuring 0.1mol/L
Aqueous solution 233.3mL (0.02333mol), 0.1mol/L chromic nitrate 175mL (0.0175mol) and 0.1mol/L aluminum nitrate
525mL (0.0525mol) is sufficiently mixed, and is taken 0.1mol/L sodium hydrate aqueous solution as precipitating reagent, is allowed using coprecipitation
Nitrate mixed solution and sodium hydrate aqueous solution react in 60 DEG C of water-baths reach 10 to pH after, be aged 10 hours；
(2) it is 7 and in normal pressure by the Washing of Filter Cake of gained to pH value by the system centrifugal treating after being aged in step (1)
Lower 80 DEG C of dryings 10 hours, obtain copper zinc chrome aluminium quaternary co-precipitate；
(3) co-precipitate obtained in step (2) is placed on 900 DEG C of Muffle kiln roasting 6h, natural cooling；
(4) salpeter solution of the mixture of gained in step (3) and aluminum oxide, boehmite, 15wt% is pressed 30：
10：1：After 5 mass ratio is well mixed, press compression molding is utilized.
The preformed catalyst prepared in 60g the present embodiment is added in fixed bed reactors, is 255 in reaction temperature
DEG C, liquid air speed 0.2h-1, methanol and aniline mol ratio be 2:Methylphenylamine is synthesized under conditions of 1.
The aniline conversion of one way is 48.37%, and methylphenylamine is selectively 99.89%.
Embodiment 3
(1) accurate copper nitrate aqueous solution 175mL (0.0175mol), the 0.1mol/L zinc nitrate water for measuring 0.1mol/L
Solution 175mL (0.0175mol), 0.1mol/L chromic nitrate 175mL (0.0175mol) and 0.1mol/L aluminum nitrate 525mL
(0.0525mol) is sufficiently mixed, and takes 0.1mol/L sodium hydrate aqueous solution as precipitating reagent, and nitrate is allowed using coprecipitation
Mixed solution and sodium hydrate aqueous solution react in 60 DEG C of water-baths reach 10 to pH after, be aged 10 hours；
(2) it is 7 and in normal pressure by the Washing of Filter Cake of gained to pH value by the system centrifugal treating after being aged in step (1)
Lower 80 DEG C of dryings 10 hours, obtain copper zinc chrome aluminium quaternary co-precipitate；
(3) co-precipitate obtained in step (2) is placed on 900 DEG C of Muffle kiln roasting 6h, natural cooling；
(4) salpeter solution of the mixture of gained in step (3) and aluminum oxide, boehmite, 15wt% is pressed 30：
10：1：After 5 mass ratio is well mixed, press compression molding is utilized.
The preformed catalyst prepared in 60g the present embodiment is added in fixed bed reactors, is 265 in reaction temperature
DEG C, liquid air speed 0.2h-1, methanol and aniline mol ratio be 3:Methylphenylamine is synthesized under conditions of 1.
The aniline conversion of one way is 92.24%, and methylphenylamine is selectively 98.04%.
Embodiment 4
(1) accurate copper nitrate aqueous solution 233.3mL (0.02333mol), the 0.1mol/L zinc nitrate for measuring 0.1mol/L
Aqueous solution 116.7mL (0.01167mol), 0.1mol/L chromic nitrate 175mL (0.0175mol) and 0.1mol/L aluminum nitrate
525mL (0.0525mol) is sufficiently mixed, and is taken 0.1mol/L sodium hydrate aqueous solution as precipitating reagent, is allowed using coprecipitation
Nitrate mixed solution and sodium hydrate aqueous solution react in 60 DEG C of water-baths reach 10 to pH after, be aged 10 hours；
(2) it is 7 and in normal pressure by the Washing of Filter Cake of gained to pH value by the system centrifugal treating after being aged in step (1)
Lower 80 DEG C of dryings 10 hours, obtain copper zinc chrome aluminium quaternary co-precipitate；
(3) co-precipitate obtained in step (2) is placed on 900 DEG C of Muffle kiln roasting 6h, natural cooling；
(4) salpeter solution of the mixture of gained in step (3) and aluminum oxide, boehmite, 15wt% is pressed 30：
10：1：After 5 mass ratio is well mixed, press compression molding is utilized.
The preformed catalyst prepared in 60g the present embodiment is added in fixed bed reactors, is 265 in reaction temperature
DEG C, liquid air speed 0.3h-1, methanol and aniline mol ratio be 3:Methylphenylamine is synthesized under conditions of 1.
The aniline conversion of one way is 93.12%, and methylphenylamine is selectively 87.58%.
Embodiment 5
(1) accurate copper nitrate aqueous solution 262.5mL (0.02625mol), the 0.1mol/L zinc nitrate for measuring 0.1mol/L
Aqueous solution 87.5mL (0.00875mol), 0.1mol/L chromic nitrate 175mL (0.0175mol) and 0.1mol/L aluminum nitrate
525mL (0.0525mol) is sufficiently mixed, and is taken 0.1mol/L sodium hydrate aqueous solution as precipitating reagent, is allowed using coprecipitation
Nitrate mixed solution and sodium hydrate aqueous solution react in 60 DEG C of water-baths reach 10 to pH after, be aged 10 hours；
(2) it is 7 and in normal pressure by the Washing of Filter Cake of gained to pH value by the system centrifugal treating after being aged in step (1)
Lower 80 DEG C of dryings 10 hours, obtain copper zinc chrome aluminium quaternary co-precipitate；
(3) co-precipitate obtained in step (2) is placed on 900 DEG C of Muffle kiln roasting 6h, natural cooling；
(4) salpeter solution of the mixture of gained in step (3) and aluminum oxide, boehmite, 15wt% is pressed 30：
10：1：After 5 mass ratio is well mixed, press compression molding is utilized.
The preformed catalyst prepared in 60g the present embodiment is added in fixed bed reactors, is 265 in reaction temperature
DEG C, liquid air speed 0.3h-1, methanol and aniline mol ratio be 4:Methylphenylamine is synthesized under conditions of 1.
The aniline conversion of one way is 95.76%, and methylphenylamine is selectively 70.10%.
Embodiment 6
On the basis of embodiment 3, the catalyst after prepared compression molding is carried out after hydrogenating reduction pretreatment, then
Come into operation, remaining operation be the same as Example 3：
(1) accurate copper nitrate aqueous solution 175mL (0.0175mol), the 0.1mol/L zinc nitrate water for measuring 0.1mol/L
Solution 175mL (0.0175mol), 0.1mol/L chromic nitrate 175mL (0.0175mol) and 0.1mol/L aluminum nitrate 525mL
(0.0525mol) is sufficiently mixed, and takes 0.1mol/L sodium hydrate aqueous solution as precipitating reagent, and nitrate is allowed using coprecipitation
Mixed solution and sodium hydrate aqueous solution react in 60 DEG C of water-baths reach 10 to pH after, be aged 10 hours；
(2) it is 7 and in normal pressure by the Washing of Filter Cake of gained to pH value by the system centrifugal treating after being aged in step (1)
Lower 80 DEG C of dryings 10 hours, obtain copper zinc chrome aluminium quaternary co-precipitate；
(3) co-precipitate obtained in step (2) is placed on after 900 DEG C of Muffle kiln roasting 6h, natural cooling, then added
Enter into fixed bed reactors, handled under the conditions of normal pressure and reduction temperature is 250 DEG C by hydrogenating reduction, be restored to no by-product
Thing is aquatic to be turned into only；
(4) mixture and aluminum oxide, boehmite, 15wt% nitric acid after hydrogenating reduction in step (3) is handled
Solution presses 30：10：1：After 5 mass ratio is well mixed, press compression molding is utilized；
The preformed catalyst prepared in 60g the present embodiment is added in fixed bed reactors, is 265 in reaction temperature
DEG C, liquid air speed 0.2h-1, methanol and aniline mol ratio be 3:Methylphenylamine is catalyzed and synthesized under conditions of 1.
As a result find that compared with Example 3, catalytic performance does not almost get a promotion, the aniline conversion of one way is
85.03%, methylphenylamine is selectively 97.52%.
Embodiment 7
(1) accurate copper nitrate aqueous solution 175mL (0.0175mol), the 0.1mol/L zinc nitrate water for measuring 0.1mol/L
Solution 175mL (0.0175mol), 0.1mol/L chromic nitrate 175mL (0.0175mol) and 0.1mol/L aluminum nitrate 525mL
(0.0525mol) is sufficiently mixed, and takes 0.1mol/L sodium hydrate aqueous solution as precipitating reagent, and nitrate is allowed using coprecipitation
Mixed solution and sodium hydrate aqueous solution react in 60 DEG C of water-baths reach 10 to pH after, be aged 10 hours；
(2) it is 7 and in normal pressure by the Washing of Filter Cake of gained to pH value by the system centrifugal treating after being aged in step (1)
Lower 80 DEG C of dryings 10 hours, obtain copper zinc chrome aluminium quaternary co-precipitate；
(3) co-precipitate obtained in step (2) is placed on 950 DEG C of Muffle kiln roasting 6h, natural cooling；
(4) salpeter solution of the mixture of gained in step (3) and aluminum oxide, boehmite, 15wt% is pressed 30：
10：1：After 5 mass ratio is well mixed, press compression molding is utilized.
The preformed catalyst prepared in 60g the present embodiment is added in fixed bed reactors, is 265 in reaction temperature
DEG C, liquid air speed 0.2h-1, methanol and aniline mol ratio be 3:Methylphenylamine is synthesized under conditions of 1.
The aniline conversion of one way is 89.63%, and methylphenylamine is selectively 98.16%.
Embodiment 8
(1) accurate copper nitrate aqueous solution 175mL (0.0175mol), the 0.1mol/L zinc nitrate water for measuring 0.1mol/L
Solution 175mL (0.0175mol), 0.1mol/L chromic nitrate 175mL (0.0175mol) and 0.1mol/L aluminum nitrate 525mL
(0.0525mol) is sufficiently mixed, and takes 0.1mol/L sodium hydrate aqueous solution as precipitating reagent, and nitrate is allowed using coprecipitation
Mixed solution and sodium hydrate aqueous solution react in 60 DEG C of water-baths reach 10 to pH after, be aged 10 hours；
(2) it is 7 and in normal pressure by the Washing of Filter Cake of gained to pH value by the system centrifugal treating after being aged in step (1)
Lower 80 DEG C of dryings 10 hours, obtain copper zinc chrome aluminium quaternary co-precipitate；
(3) co-precipitate obtained in step (2) is placed on 1000 DEG C of Muffle kiln roasting 6h, natural cooling；
(4) salpeter solution of the mixture of gained in step (3) and aluminum oxide, boehmite, 15wt% is pressed 30：
10：1：After 5 mass ratio is well mixed, press compression molding is utilized.
The preformed catalyst prepared in 60g the present embodiment is added in fixed bed reactors, is 265 in reaction temperature
DEG C, liquid air speed 0.2h-1, methanol and aniline mol ratio be 3:Methylphenylamine is synthesized under conditions of 1.
The aniline conversion of one way is 82.53%, and methylphenylamine is selectively 98.25%.
Claims (8)
1. a kind of preparation method of the catalyst synthesized for methylphenylamine, it is characterised in that：Described preparation method is,
(1) mantoquita, zinc salt, chromic salts, aluminium salt are made into mixed liquor, the mixed liquor is adjusted to alkalescence and is aged；
(2) by the system centrifugal treating after being aged in step (1), by the Washing of Filter Cake of gained and drying, copper zinc chrome aluminium four is obtained
First co-precipitate；
(3) it is the copper zinc chrome aluminium four with spinel structure by the copper zinc chrome aluminium quaternary co-precipitate calcination obtained in step (2)
First catalyst；
(4) the copper zinc chrome aluminium four-way catalyst of gained in step (3) is mixed with aluminum oxide, boehmite and salpeter solution
Even rear compression molding.
2. the preparation method of the catalyst synthesized as claimed in claim 1 for methylphenylamine, it is characterised in that：Step
(1) in, mantoquita, zinc salt, chromic salts, aluminium salt are according to copper nitrate, zinc nitrate, chromic nitrate, aluminum nitrate 1~3：1~3：1：3 mol ratio
Mixing.
3. the preparation method of the catalyst synthesized as claimed in claim 1 for methylphenylamine, it is characterised in that：Step
(1) in, regulation mixed liquor specifically uses the pH value of 0.1mol/L sodium hydrate aqueous solution regulation mixed liquor for 10 when being alkalescence,
Digestion time is 10 hours.
4. the preparation method of the catalyst synthesized as claimed in claim 1 for methylphenylamine, it is characterised in that：Step
(2) it is 7 and in the lower 80 DEG C of dryings of normal pressure 10 hours by the Washing of Filter Cake of gained to pH value in.
5. the preparation method of the catalyst synthesized as claimed in claim 1 for methylphenylamine, it is characterised in that：Step
(3) in, co-precipitate calcination 6 hours at 900~1000 DEG C.
6. the preparation method of the catalyst synthesized as claimed in claim 1 for methylphenylamine, it is characterised in that：Step
(4) Solute mass fraction of salpeter solution described in is 15wt%.
7. the preparation method of the catalyst synthesized as claimed in claim 1 for methylphenylamine, it is characterised in that：Step
(4) in, copper zinc chrome aluminium four-way catalyst, aluminum oxide, boehmite, salpeter solution press 30：10：1：5 mass ratio mixing is equal
It is even.
8. a kind of catalyst prepared such as any one of claim 1 to 7 methods described is in vapor phase method synthesis methylphenylamine technique
In application, it is characterised in that：The catalyst is placed in fixed bed reactors, normal pressure, 245~265 DEG C of reaction temperature,
0.1~0.3h of liquid air speed-1, aniline and methanol molar ratio 1：Reaction synthesis methylphenylamine under conditions of 2~4.
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| RU2346740C1 (en) * | 2007-08-22 | 2009-02-20 | Институт Катализа Им. Г.К. Борескова Сибирского Отделения Российской Академии Наук | Catalyst and method of obtaining n-methylaniline |
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| RU2346740C1 (en) * | 2007-08-22 | 2009-02-20 | Институт Катализа Им. Г.К. Борескова Сибирского Отделения Российской Академии Наук | Catalyst and method of obtaining n-methylaniline |
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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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Application publication date: 20170901 Assignee: Shandong Zhengzun Technology Service Co.,Ltd. Assignor: CHANGZHOU University Contract record no.: X2023980053025 Denomination of invention: Preparation method and application of a catalyst for the synthesis of N-methylaniline Granted publication date: 20200320 License type: Common License Record date: 20231220 |