CN107020083A - A kind of 1 nitroanthraquinone Hydrogenation is for 1 amino anthraquinones catalyst and its preparation method and application - Google Patents
A kind of 1 nitroanthraquinone Hydrogenation is for 1 amino anthraquinones catalyst and its preparation method and application Download PDFInfo
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- CN107020083A CN107020083A CN201710190290.4A CN201710190290A CN107020083A CN 107020083 A CN107020083 A CN 107020083A CN 201710190290 A CN201710190290 A CN 201710190290A CN 107020083 A CN107020083 A CN 107020083A
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
Abstract
The invention belongs to the catalyst technology in field of fine chemical, and in particular to a kind of 1 nitroanthraquinone Hydrogenation is for 1 amino anthraquinones catalyst and its preparation method and application.Mesoporous carbon is added in ethylenediamine solution and soaked, then using the salt solution impregnated carrier mesoporous carbon containing palladium and silver, reduces, washs, filtering obtains Pd Ag/ gold/mesoporous carbon catalysts.Above-mentioned hydrogenation catalyst is used for 1 nitroanthraquinone Hydrogenation for 1 amino anthraquinones, and reaction condition is gentle, and selectivity of product is high.
Description
Technical field
The invention belongs to the catalyst technology in field of fine chemical, and in particular to a kind of 1- nitroanthraquinones Hydrogenation is for 1-
Amino anthraquinones catalyst and its preparation method and application.
Background technology
Anthraquinone dye is the second major class dyestuff after azo based dye, and wherein 1- amino anthraquinones is synthesis anthraquinone series dyes
Important intermediate, its purposes is most wide, and consumption is also maximum, is production bromamine acid, the primary raw material of pyrazoles anthraquinone.Market is to 1- ammonia
The demand of base anthraquinone is continuously increased, and the 1- amino anthraquinones yield of especially high-quality far can not meet the market demand.
Traditional production technology has sulfonation ammonolysis process and vulcanization alkaline process.Sulfonation ammonolysis process post-processes the discharge for having mercury waste water,
The health of serious infringement operating personnel, has not been used at present.Vulcanization alkaline process is the master that domestic production 1- amino anthraquinones is used
Technique is wanted, the 1- amino anthraquinones impurity contents produced with vulcanization alkaline process reducing process are higher, and need complicated purifying technique, separation
Substantial amounts of sodium sulfite and sodium hydrosulfite are consumed in subtractive process so that the process waste liquor processing cost is high, easily causes environmental pollution.
As environmental protection pressure increases, it is that production 1- amino anthraquinones is badly in need of solution to find economic and environment-friendly friendly process
Certainly the problem of.At present, the friendly process of production 1- amino anthraquinones mainly has：Catalytic hydrogenating reduction method, hydrazine hydrate reduction method and electricity
Chemical reduction method etc., wherein, the advantage such as catalytic hydrogenating reduction method has a selectivity good, product purity is high, therefore receive much concern.
But when utilizing 1- nitroanthraquinone Preparation of 1-aminoanthraquinone by catalytic hydrogenation, due to this aromatic nitro of 1- nitroanthraquinones
Compound molecule is larger, and containing two C=O double bonds, it is anti-in hydrogenating reduction compared to other kinds of aromatic nitro compound
Much lower on the activity and selectivity answered, catalysis difficulty is big, and catalyst is easily inactivated, thus catalyst amount is big, cost is high,
Industrialization can not be realized with conventional catalyst, this is also to prepare 1- amino anthraquinones with 1- nitroanthraquinone catalytic hydrogenations method so far not having
Realize industrialized reason.
The content of the invention
The present invention for the aspect such as associated catalysts poor selectivity, easy in inactivation, cost height of prior art deficiency there is provided
A kind of 1- nitroanthraquinones Hydrogenation is for 1- amino anthraquinones catalyst, and the catalyst includes carrier and active component, and carrier is warp
Cross ethylenediamine pretreatment mesoporous carbon, active component be palladium and silver,
Wherein, the catalyst components are that palladium 1%~10%, silver 1%~5%, surplus are warp by mass percentage
The mesoporous carbon of ethylenediamine pretreatment is crossed,
Mesoporous carbon carrier can use existing commodity, can also be prepared with prior art, it is desirable to which the pore volume of mesoporous carbon is
1.5-2.0mL/g, specific surface area are 1000-2000m2/ g, bore dia are 3-8nm.
Present invention also offers a kind of preparation method of above-mentioned catalyst,
(1) mesoporous carbon is added and fully soaked in ethylenediamine solution, then with distillation water washing, filtered,
The modification of ethylenediamine is conducive to strengthening mesoporous carbon and active substance palladium, the interaction of silver, is lived so as to improve catalysis
Property,
Wherein, the mass concentration of ethylenediamine is 1~10wt% in ethylenediamine solution, and soak time is 1~24 hour；
(2) mesoporous carbon pre-processed by step (1) is sufficiently impregnated using the solution containing palladium salt and silver salt, then with formaldehyde also
Original, then with distillation water washing, suction filtration, drying obtain Pd-Ag/ gold/mesoporous carbon catalysts,
In solution containing palladium salt and silver salt, the mass percent of palladium element is 0.2~2%, the mass percent of silver element
For 0.2~1%, dip time is 2~12h.
Present invention also offers a kind of tool of above-mentioned catalyst when being catalyzed 1- nitroanthraquinones Hydrogenation for 1- amino anthraquinones
Body application：
Using 1- nitroanthraquinones as raw material, under conditions of the presence of solvent, auxiliary agent and catalyst, it is passed through hydrogen and be catalyzed instead
1- amino anthraquinones should be prepared,
The temperature of catalytic reaction is 40~120 DEG C, and the pressure for being passed through hydrogen is 0.1~2MPa,
Solvent be water, methanol, isopropanol, ethylbenzene, methyl phenyl ethers anisole, dimethylformamide in one kind, 1- nitroanthraquinones with it is molten
The mass ratio of agent is 1: 5~1: 20,
Auxiliary agent is ammonium metavanadate, and consumption is the 0.5%~5% of 1- nitroanthraquinone quality；Catalyst amount is 1- nitroanthracenes
The 0.5%~5% of quinone quality.
The beneficial effects of the present invention are：The active metal stability of catalyst is significantly improved in the present invention, hydrogenation process
Yield further improve, catalyst amount can be obviously reduced, with industrial prospect；
Catalyst carrier selects mesoporous carbon, and its suitable duct is conducive to reducing inside diffusional resistance, improves reaction rate, shows
Work slows down the catalyst inactivation caused by hole plug, so that catalyst stability is improved, compared with absorbent charcoal carrier, target product
Yield is significantly improved；Compared with inorganic oxide carrier (such as aluminum oxide), active component palladium and silver are easily recycled in dead catalyst；
So that containing palladium and containing silver salt solution as the presoma of catalyst active component, preparation method is simple, it is easy to industrialize.
Embodiment
The preparation method of loaded catalyst in following embodiment：
(1) mesoporous carbon is added in ethylenediamine solution and soaked 15 hours, then with distillation water washing, filtered；
(2) mesoporous carbon 8 hours of step (1) pretreatment is dipped through using the solution containing palladium nitrate and silver nitrate, then is used
Excessive formaldehyde is fully reduced under room temperature (25 DEG C), and then with distillation water washing, suction filtration, drying obtain Pd-Ag/ mesoporous carbons
Catalyst, the content of Pd and Ag in catalyst is controlled according to the mass concentration of palladium element and silver element in solution.
Embodiment 1
In the autoclave with stirring, adding 10%Pd-1%Ag/ gold/mesoporous carbon catalysts, (mesoporous carbon uses quality in advance
Concentration is handled for 5wt% ethylenediamine solution；Pd and Ag percentage each accounts for the percentage of catalyst gross mass for it, under
0.01g, 1- nitroanthraquinone 2.0g, distilled water 10ml, ammonium metavanadate 0.01g together), close reactor, use nitrogen displacement reactor
In air three times, then with the nitrogen three times in hydrogen replacement reaction kettle, being then re-filled with hydrogen makes the reaction pressure of reactor
0.5MPa is reached, heating response kettle makes reaction temperature reach 120 DEG C, start stirring, isothermal reaction until pressure is no longer dropped to
Only, taking-up reaction product, Filtration of catalyst, using liquid-phase chromatographic analysis, it (is selectively feeling the pulse with the finger-tip that analysis result, which is listed in table 1,
Product 1- amino anthraquinones percentage shared in all products (target product+various accessory substances) is marked, similarly hereinafter；Conversion ratio × choosing
Selecting property=yield).
Embodiment 2
In the autoclave with stirring, adding 8%Pd-1%Ag/ gold/mesoporous carbon catalysts, (mesoporous carbon uses quality in advance
Concentration for 1wt% ethylenediamine solution handle) 0.08g, 1- nitroanthraquinone 2.0g, methanol 40ml, ammonium metavanadate 0.08g, close
Reactor is closed, with the air three times in nitrogen displacement reactor, then with the nitrogen three times in hydrogen replacement reaction kettle, is then filled again
Entering hydrogen makes the reaction pressure of reactor reach 1.0MPa, and heating response kettle makes reaction temperature reach 100 DEG C, starts stirring, permanent
Temperature reaction takes out reaction product, Filtration of catalyst, using liquid-phase chromatographic analysis, analysis untill pressure no longer declines
As a result it is listed in table 1.
Embodiment 3
In the autoclave with stirring, adding 5%Pd-3%Ag/ gold/mesoporous carbon catalysts, (mesoporous carbon uses quality in advance
Concentration for 10wt% ethylenediamine solution handle) 0.02g, 1- nitroanthraquinone 2.0g, isopropanol 40ml, ammonium metavanadate 0.02g,
Reactor is closed, with the air three times in nitrogen displacement reactor, then with the nitrogen three times in hydrogen replacement reaction kettle, Ran Houzai
Being filled with hydrogen makes the reaction pressure of reactor reach 2.0MPa, and heating response kettle makes reaction temperature reach 100 DEG C, starts stirring,
Isothermal reaction takes out reaction product untill pressure no longer declines, and Filtration of catalyst, using liquid-phase chromatographic analysis, divides
Analysis result is listed in table 1.
Embodiment 4
In the autoclave with stirring, adding 5%Pd-3%Ag/ gold/mesoporous carbon catalysts, (mesoporous carbon uses quality in advance
Concentration for 10wt% ethylenediamine solution handle) 0.02g, 1- nitroanthraquinone 2.0g, isopropanol 40ml, ammonium metavanadate 0.02g,
Reactor is closed, with the air three times in nitrogen displacement reactor, then with the nitrogen three times in hydrogen replacement reaction kettle, Ran Houzai
Being filled with hydrogen makes the reaction pressure of reactor reach 1.0MPa, and heating response kettle makes reaction temperature reach 80 DEG C, starts stirring, permanent
Temperature reaction takes out reaction product, Filtration of catalyst, using liquid-phase chromatographic analysis, analysis untill pressure no longer declines
As a result it is listed in table 1.
Embodiment 5
In the autoclave with stirring, adding 5%Pd-4%Ag/ gold/mesoporous carbon catalysts, (mesoporous carbon uses quality in advance
Concentration for 2wt% ethylenediamine solution handle) 0.02g, 1- nitroanthraquinone 2.0g, ethylbenzene 40ml, ammonium metavanadate 0.02g, close
Reactor is closed, with the air three times in nitrogen displacement reactor, then with the nitrogen three times in hydrogen replacement reaction kettle, is then filled again
Entering hydrogen makes the reaction pressure of reactor reach 0.2MPa, and heating response kettle makes reaction temperature reach 60 DEG C, starts stirring, constant temperature
Reaction takes out reaction product, Filtration of catalyst, using liquid-phase chromatographic analysis, analysis knot untill pressure no longer declines
Fruit is listed in table 1.
Embodiment 6
In the autoclave with stirring, adding 3%Pd-4%Ag/ gold/mesoporous carbon catalysts, (mesoporous carbon uses quality in advance
Concentration for 8wt% ethylenediamine solution handle) 0.02g, 1- nitroanthraquinone 2.0g, methyl phenyl ethers anisole 20ml, ammonium metavanadate 0.02g,
Reactor is closed, with the air three times in nitrogen displacement reactor, then with the nitrogen three times in hydrogen replacement reaction kettle, Ran Houzai
Being filled with hydrogen makes the reaction pressure of reactor reach 1.0MPa, and heating response kettle makes reaction temperature reach 100 DEG C, starts stirring,
Isothermal reaction takes out reaction product untill pressure no longer declines, and Filtration of catalyst, using liquid-phase chromatographic analysis, divides
Analysis result is listed in table 1.
Embodiment 7
In the autoclave with stirring, adding 1%Pd-5%Ag/ gold/mesoporous carbon catalysts, (mesoporous carbon uses quality in advance
Concentration for 5wt% ethylenediamine solution handle) 0.02g, 1- nitroanthraquinone 2.0g, dimethylformamide 40ml, ammonium metavanadate
0.02g, closes reactor, with the air three times in nitrogen displacement reactor, then with the nitrogen three times in hydrogen replacement reaction kettle,
Then being re-filled with hydrogen makes the reaction pressure of reactor reach 1.0MPa, and heating response kettle makes reaction temperature reach 40 DEG C, beginning
Stirring, isothermal reaction takes out reaction product, Filtration of catalyst, using liquid chromatogram point untill pressure no longer declines
Analysis, analysis result is listed in table 1.
Comparative example 1
Mesoporous carbon is not handled with ethylenediamine solution in advance, and remaining operates equal be the same as Example 3：
In the autoclave with stirring, 5%Pd-3%Ag/ gold/mesoporous carbon catalyst 0.02g, 1- nitroanthraquinones are added
2.0g, isopropanol 40ml, ammonium metavanadate 0.02g, close reactor, with the air three times in nitrogen displacement reactor, then use hydrogen
Nitrogen in gas replacement reaction kettle three times, being then re-filled with hydrogen makes the reaction pressure of reactor reach 2.0MPa, heating response
Kettle makes reaction temperature reach 100 DEG C, starts stirring, and isothermal reaction takes out reaction product, filtering untill pressure no longer declines
Catalyst is removed, using liquid-phase chromatographic analysis, analysis result is listed in table 1.
Comparative example 2
On the basis of above-mentioned comparative example 1, silver will be saved in catalyst active component：
In the autoclave with stirring, 5%Pd/ gold/mesoporous carbon catalyst 0.02g, 1- nitroanthraquinones 2.0g is added, different
Propyl alcohol 40ml, ammonium metavanadate 0.02g, close reactor, with the air three times in nitrogen displacement reactor, then are replaced with hydrogen anti-
The nitrogen three times in kettle is answered, being then re-filled with hydrogen makes the reaction pressure of reactor reach 2.0MPa, and heating response kettle makes reaction
Temperature reaches 100 DEG C, starts stirring, and isothermal reaction takes out reaction product, be filtered to remove catalysis untill pressure no longer declines
Agent, using liquid-phase chromatographic analysis, analysis result is listed in table 1.
Comparative example 3
On the basis of above-mentioned comparative example 2, mesoporous carbon is replaced using conventional activated carbon：
In the autoclave with stirring, 5%Pd/ activated-carbon catalyst 0.02g, 1- nitroanthraquinones 2.0g is added, different
Propyl alcohol 40ml, ammonium metavanadate 0.02g, close reactor, with the air three times in nitrogen displacement reactor, then are replaced with hydrogen anti-
The nitrogen three times in kettle is answered, being then re-filled with hydrogen makes the reaction pressure of reactor reach 2.0MPa, and heating response kettle makes reaction
Temperature reaches 100 DEG C, starts stirring, and isothermal reaction takes out reaction product, be filtered to remove catalysis untill pressure no longer declines
Agent, using liquid-phase chromatographic analysis, analysis result is listed in table 1.
Comparative example 4
Auxiliary agent ammonium metavanadate is not added in hydrogenation process, remaining operates equal be the same as Example 3：
In the autoclave with stirring, adding 5%Pd-3%Ag/ gold/mesoporous carbon catalysts, (mesoporous carbon uses quality in advance
Concentration is handled for 10wt% ethylenediamine solution) 0.02g, 1- nitroanthraquinone 2.0g, isopropanol 40ml, close reactor, use
Air in nitrogen displacement reactor three times, then with the nitrogen three times in hydrogen replacement reaction kettle, being then re-filled with hydrogen makes instead
Answer the reaction pressure of kettle to reach 2.0MPa, heating response kettle makes reaction temperature reach 100 DEG C, start stirring, isothermal reaction until
Untill pressure no longer declines, taking-up reaction product, Filtration of catalyst, using liquid-phase chromatographic analysis, analysis result is listed in table
1。
Table 1
| 1- nitroanthraquinones conversion ratio (%) | 1- amino anthraquinones selectivity (%) | |
| Embodiment 1 | 99.1 | 93.3 |
| Embodiment 2 | 100 | 96.2 |
| Embodiment 3 | 100 | 99.1 |
| Embodiment 4 | 99.9 | 99.6 |
| Embodiment 5 | 92.3 | 99.8 |
| Embodiment 6 | 88.9 | 99.3 |
| Embodiment 7 | 73.6 | 99.4 |
| Comparative example 1 | 70.6 | 95.4 |
| Comparative example 2 | 93.5 | 60.8 |
| Comparative example 3 | 21.2 | 64.6 |
| Comparative example 4 | 98.2 | 63.5 |
Table 1 illustrates that the load type bimetal catalyst prepared by the solution of the present invention is reacted the liquid-phase hydrogenatin of 1- nitroanthraquinones
There is higher selectivity with higher activity and to 1- amino anthraquinones, and preparation process is simple, is more preferable 1-
The catalyst of nitroanthraquinone liquid phase catalytic hydrogenation 1- amino anthraquinones.
Claims (9)
1. a kind of 1- nitroanthraquinones Hydrogenation is for 1- amino anthraquinones catalyst, it is characterised in that：Described catalyst includes carrying
Body and active component, described carrier are the mesoporous carbon pre-processed by ethylenediamine, and described active component is palladium and silver.
2. catalyst as claimed in claim 1, it is characterised in that：Described catalyst components are calculated by mass percentage
For palladium 1%~10%, silver 1%~5%, surplus are the mesoporous carbon pre-processed by ethylenediamine.
3. a kind of preparation method of catalyst as claimed in claim 1, it is characterised in that：Described preparation method is,
(1) mesoporous carbon is added and fully soaked in ethylenediamine solution, then with distillation water washing, filtered；
(2) mesoporous carbon pre-processed by step (1) is sufficiently impregnated using the solution containing palladium salt and silver salt, then is reduced with formaldehyde,
Then with distillation water washing, suction filtration, drying obtain Pd-Ag/ gold/mesoporous carbon catalysts.
4. the preparation method of catalyst as claimed in claim 3, it is characterised in that：In step (1), second in ethylenediamine solution
The mass concentration of diamines is 1~10wt%, and soak time is 1~24 hour.
5. the preparation method of catalyst as claimed in claim 3, it is characterised in that：It is molten containing palladium salt and silver salt in step (2)
In liquid, the mass percent of palladium element is 0.2~2%, and the mass percent of silver element is 0.2~1%, dip time is 2~
12h。
6. a kind of application of catalyst as claimed in claim 1, it is characterised in that：Described application is, with 1- nitroanthraquinones
For raw material, under conditions of the presence of solvent, auxiliary agent and catalyst, it is passed through hydrogen and carries out catalytic reaction preparation 1- amino anthraquinones.
7. the application of catalyst as claimed in claim 6, it is characterised in that：The temperature of catalytic reaction is 40~120 DEG C, is passed through
The pressure of hydrogen is 0.1~2MPa.
8. the application of catalyst as claimed in claim 6, it is characterised in that：Described solvent is water, methanol, isopropanol, second
The mass ratio of one kind in benzene, methyl phenyl ethers anisole, dimethylformamide, 1- nitroanthraquinones and the solvent is 1: 5~1: 20.
9. the application of catalyst as claimed in claim 6, it is characterised in that：Described auxiliary agent is ammonium metavanadate, and consumption is 1-
The 0.5%~5% of nitroanthraquinone quality.
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Cited By (5)
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| CN107497426A (en) * | 2017-08-30 | 2017-12-22 | 江苏大学 | A kind of preparation method and applications of palladium/silver alloy nanocatalyst |
| CN108276312A (en) * | 2018-02-06 | 2018-07-13 | 河北建新化工股份有限公司 | A kind of preparation method of metanilic acid |
| CN108295850A (en) * | 2018-01-22 | 2018-07-20 | 江苏欣诺科催化剂有限公司 | A kind of catalyst and its catalysis process preparing amino anthraquinones |
| CN112239404A (en) * | 2019-07-17 | 2021-01-19 | 中国石油化工股份有限公司 | Hydrofining reaction and catalyst therefor |
| CN113304763A (en) * | 2021-06-10 | 2021-08-27 | 青岛福凯橡塑新材料有限公司 | Catalyst for preparing aminoanthraquinone through hydrogenation, preparation method and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107497426A (en) * | 2017-08-30 | 2017-12-22 | 江苏大学 | A kind of preparation method and applications of palladium/silver alloy nanocatalyst |
| CN107497426B (en) * | 2017-08-30 | 2020-06-09 | 江苏大学 | Preparation method and application of palladium/silver alloy nano catalyst |
| CN108295850A (en) * | 2018-01-22 | 2018-07-20 | 江苏欣诺科催化剂有限公司 | A kind of catalyst and its catalysis process preparing amino anthraquinones |
| CN108295850B (en) * | 2018-01-22 | 2020-10-02 | 江苏欣诺科催化剂有限公司 | Catalyst for preparing aminoanthraquinone and catalytic method thereof |
| CN108276312A (en) * | 2018-02-06 | 2018-07-13 | 河北建新化工股份有限公司 | A kind of preparation method of metanilic acid |
| CN108276312B (en) * | 2018-02-06 | 2020-11-06 | 河北建新化工股份有限公司 | Preparation method of m-aminobenzene sulfonic acid |
| CN112239404A (en) * | 2019-07-17 | 2021-01-19 | 中国石油化工股份有限公司 | Hydrofining reaction and catalyst therefor |
| CN113304763A (en) * | 2021-06-10 | 2021-08-27 | 青岛福凯橡塑新材料有限公司 | Catalyst for preparing aminoanthraquinone through hydrogenation, preparation method and application thereof |
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| CN107020083B (en) | 2019-06-04 |
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