CN106944123A - A kind of preparation method and its usage of hydrogenation catalyst - Google Patents
A kind of preparation method and its usage of hydrogenation catalyst Download PDFInfo
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- CN106944123A CN106944123A CN201710216340.1A CN201710216340A CN106944123A CN 106944123 A CN106944123 A CN 106944123A CN 201710216340 A CN201710216340 A CN 201710216340A CN 106944123 A CN106944123 A CN 106944123A
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- nickel
- nitrogen
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- hydrogenation catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
Abstract
The invention provides a kind of preparation method and its usage of hydrogenation catalyst, preparation method is：（1）Using cerium oxide as carrier to load metal nickel salt, then roasting obtains the nickel oxide of cerium oxide load in air atmosphere；（2）Then by step（1）Obtained compound is uniformly mixed with ethylenediamine and carbon tetrachloride, and back flow reaction obtains coating the catalyst precarsor of polymer with nitrogen in dimethylbenzene；Or by step（1）Obtained compound is mixed to get catalyst precarsor with glucose and nitrogen-containing compound；（3）By catalyst precarsor in an inert atmosphere by 500 1000 DEG C of high-temperature roastings so as to obtain the hydrogenation catalyst that nitrogen-doped carbon coats metallic nickel.The catalyst is used to be catalyzed the purposes that hydrogenation of chloronitrobenzene synthesizes para-aminophenol, and nitrobenzene conversion rate and para-aminophenol selectively can reach 100%.
Description
Technical field
The use of para-aminophenol is synthesized the present invention relates to a kind of preparation method of catalyst, and its catalysis hydrogenation of chloronitrobenzene
On the way.
Background technology
Para-aminophenol is a kind of important organic intermediate, is widely used in the fields such as medicine, dyestuff and rubber.Mesh
Before, the process of industrial production para-aminophenol is mainly in strongly acidic solution by being catalyzed hydrogenation of chloronitrobenzene and a step is made
, the catalyst used in this process conditions is typically the noble metal platinum or palladium catalyst of load, and the conversion ratio of nitrobenzene can
Up to 90%, while the selectivity of para-aminophenol is about 85%.But (be typically 15wt.% in the reaction medium of highly acid
Aqueous sulfuric acid), there is the possibility that is poisoned in noble metal and active component can also be lost in, so as to make to catalyst
Adverse effect is brought with the control aspect in life-span and production cost.
In order to improve the production technology under this strong acidic condition, people it is also proposed that substituting fluid sulphuric acid in water with solid acid
Catalysis hydrogenation of chloronitrobenzene synthesis para-aminophenol is carried out in solution, so that the loss of active component is reduced, but this technique is set
Meter is needed to add substantial amounts of solid acid, and noble metal active component is still in sour environment, still can not be kept away
Exempt from the loss of active component；In addition, the selectivity of para-aminophenol will be reduced instead of sulfuric acid using solid acid.
Therefore, explore a kind of catalyst of the new structure based on base metal and seem significant.
The content of the invention
It is an object of the invention to provide a kind of preparation method and its usage of hydrogenation catalyst, the hydrogenation catalyst is based on
Base metal is obtained, catalysis hydrogenation of chloronitrobenzene synthesis para-aminophenol, with high selectivity.
In order to realize foregoing invention purpose, present invention employs following technical scheme：
A kind of preparation method of hydrogenation catalyst, step is as follows：
(1) using cerium oxide as carrier to load metal nickel salt, then roasting obtains the oxygen of cerium oxide load in air atmosphere
Change nickel；Roasting time is 4 hours in air atmosphere；
(2) compound and then by step (1) obtained is uniformly mixed with ethylenediamine and carbon tetrachloride, is flowed back in dimethylbenzene
Reaction obtains coating the catalyst precarsor of polymer with nitrogen；Or the compound for obtaining step (1) and glucose and nitrogen
Compound is mixed to get catalyst precarsor；
(3) catalyst precarsor is coated by 500-1000 DEG C of high-temperature roasting so as to obtain nitrogen-doped carbon in an inert atmosphere
Preferred 600-800 DEG C of sintering temperature in the hydrogenation catalyst of metallic nickel, the step.
The nickel salts are nickel nitrate, nickel chloride or nickel acetate；
With cerium oxide carried metal nickel salt in step (1), the load capacity of nickel is 1-14%, preferably 4-8%；
The nitrogen-containing compound is urea, melamine, dicyandiamide, pyrroles, polypyrrole, Lauxite and polyvinyl pyrrole
One or more in alkanone.
In step (2), the nickel oxide of relative to every gram cerium oxide load, the mass ratio of ethylenediamine and carbon tetrachloride is 1:1-
1:10, preferably 1:2-1:4；
In step (2), the nickel oxide of relative to every gram cerium oxide load, the mass ratio of glucose and nitrogen-containing compound is 1:
4-1:20, preferably 1:4-1:8.
Above-mentioned catalyst is used to be catalyzed the purposes that hydrogenation of chloronitrobenzene synthesizes para-aminophenol, nitrobenzene conversion rate and to amino
Phenol selectivity can reach 100%.
The present invention obtains a kind of hydrogenation catalyst based on base metal, and uses it for catalysis hydrogenation of chloronitrobenzene synthesis to ammonia
Base phenol, shows excellent catalytic performance.The process cost is cheap, and technique is simple, for exploitation catalysis hydrogenation of chloronitrobenzene synthesis
The high performance catalyst of para-aminophenol provides new thinking.
Embodiment
Technical scheme is illustrated below with reference to embodiment：
The acquisition of carrier cerium oxide employed in the present embodiment can be obtained without particular/special requirement using conventional method.
Specifically, the carrier cerium oxide is obtained in the following manner：Weigh 16.88g NaOH to be dissolved in 30mL water, so
After weigh 1.96g cerous nitrates add 40mL water in stirring dissolve cerous nitrate, the sodium hydroxide solution configured is slowly added to
In the cerous nitrate aqueous solution and continue stirring, 100 DEG C reaction 24 hours after be cooled to room temperature, after centrifuge washing is multiple vacuum do
It is dry to produce carrier cerium oxide.
Catalysis hydrogenation of chloronitrobenzene synthesis para-aminophenol is carried out in the following manner, and 50.0mg is sequentially added in autoclave
The aqueous sulfuric acid of catalyst, 100.0mg nitrobenzene and 25.0mL 15wt.%, is then charged with inert gas (such as nitrogen) displacement
Air in reactor, is filled with 1.0Mpa hydrogen after being repeated several times, persistently stirred at 120 DEG C and stop heating after 2 hours, treated
The hydrogen drained after room temperature in reactor is cooled to, catalyst is obtained with being recovered by filtration after ammoniacal liquor neutralization reaction liquid, then uses first
Benzene extraction filtrate obtains organic phase and with the organic phase composition of efficient liquid phase chromatographic analysis.
Embodiment 1
(1) cerium oxide (CeO2) carrier is by broken sieving, selection 20-40 mesh, incipient impregnation nickel nitrate aqueous solution is obtained
The sample for being 6wt.% to the load capacity of nickel；Stand after a period of time, 80 DEG C are dried under vacuum to after constant weight 450 in air atmosphere
Roasting obtains the nickel oxide (NiO/CeO of cerium oxide load for 4 hours at DEG C2)；
(2) 1g NiO/CeO are taken2Add in round-bottomed flask, sequentially add 2.0g ethylenediamines and 4.0g carbon tetrachloride and 80mL
Dimethylbenzene, be first warming up to 90 DEG C reaction 4 hours after be warming up to again 140 DEG C continue react 4 hours, then stop heating being cooled to
Sediment and drying are centrifuged out after room temperature, grinding obtains powdered product；
(3) 600 DEG C of roastings obtain black grained catalyst (CN/Ni/CeO for 6 hours and then in nitrogen atmosphere2)。
Catalysis hydrogenation of chloronitrobenzene synthesis para-aminophenol is used it for, wherein nitrobenzene conversion rate is 99%.P-aminophenyl
Phenol is selectively 100%.
Embodiment 2-5 has investigated catalyst hydrogenation of chloronitrobenzene synthesis pair obtained by the load capacity of different nickel in step (1)
The influence of amino-phenol, is shown in Table 1, nickel salts are nickel nitrate, nickel chloride or nickel acetate, remaining be the same as Example 1：
Table 1
Embodiment 6-8 has investigated catalyst nitre obtained by the mass ratio of different ethylenediamines and carbon tetrachloride in step (2)
Base benzene hydrogenation synthesizes the influence of para-aminophenol, is shown in Table 2, remaining be the same as Example 1：
Table 2
Embodiment 9-11 has investigated in step (3) catalyst nitrobenzene obtained by treatment temperature in different nitrogen atmospheres and added
Hydrogen synthesizes the influence of para-aminophenol, is shown in Table 3, remaining be the same as Example 1：
Table 3
| Embodiment | Embodiment 1 | Embodiment 9 | Embodiment 10 | Embodiment 11 |
| The temperature handled in nitrogen atmosphere/DEG C | 600℃ | 500℃ | 800℃ | 1000℃ |
| Nitrobenzene conversion rate % | 99% | 89% | 100% | 100% |
| Para-aminophenol selectivity % | 100% | 100% | 93% | 48% |
Embodiment 12
(1) cerium oxide (CeO2) carrier is by broken sieving, selection 20-40 mesh, incipient impregnation nickel nitrate aqueous solution is obtained
The sample for being 6wt.% to the load capacity of nickel, stands after a period of time, 80 DEG C are dried under vacuum to after constant weight 450 in air atmosphere
Roasting obtains the nickel oxide (NiO/CeO of cerium oxide load for 4 hours at DEG C2)；
(2) 1g NiO/CeO are taken2, 0.5g glucose and 2.0g urea, ball milling is allowed to well mixed；
(3) 600 DEG C of roastings obtain black grained catalyst (CN/Ni/CeO for 6 hours and then in nitrogen atmosphere2).By its
For being catalyzed hydrogenation of chloronitrobenzene synthesis para-aminophenol, wherein nitrobenzene conversion rate is 99%.Para-aminophenol is selectively
100%.
Embodiment 13
It is identical with the method for embodiment 12, the difference is that the consumption of glucose is 0.2g, obtained catalyst nitro
Benzene hydrogenation synthesizes para-aminophenol, and wherein nitrobenzene conversion rate is 100%, and para-aminophenol is selectively 43%.
Embodiment 13-16 has investigated catalyst obtained by the mass ratio of different glucose and nitrogen-containing compound in step (2) and urged
Change the influence that hydrogenation of chloronitrobenzene synthesizes para-aminophenol, be shown in Table 4, remaining be the same as Example 12, wherein nitrogen-containing compound are urea, three
Any one in poly cyanamid, dicyandiamide, pyrroles, polypyrrole, Lauxite and polyvinylpyrrolidone：
Table 4
Embodiment 17,18 has investigated in step (3) catalyst nitrobenzene obtained by treatment temperature in different nitrogen atmospheres
The influence of hydrogenation synthesis para-aminophenol, is shown in Table 5, remaining be the same as Example 12：
Table 5
| Embodiment | Embodiment 12 | Embodiment 17 | Embodiment 18 |
| The temperature handled in nitrogen atmosphere/DEG C | 600℃ | 1000℃ | 500℃ |
| Nitrobenzene conversion rate % | 99% | 100% | 82% |
| Para-aminophenol selectivity % | 100% | 82% | 96% |
Embodiment 19-21 has investigated catalyst hydrogenation of chloronitrobenzene synthesis obtained by the load capacity of different nickel in step (1)
The influence of para-aminophenol, is shown in Table 6, remaining be the same as Example 12：
Table 6
Claims (6)
1. a kind of preparation method of hydrogenation catalyst, it is characterised in that step is as follows：
（1）Using cerium oxide as carrier to load metal nickel salt, then roasting obtains the nickel oxide of cerium oxide load in air atmosphere；
（2）Then by step（1）Obtained compound is uniformly mixed with ethylenediamine and carbon tetrachloride, the back flow reaction in dimethylbenzene
Obtain coating the catalyst precarsor of polymer with nitrogen；Or by step（1）Obtained compound and glucose and nitrogen-containing compound
It is mixed to get catalyst precarsor；
（3）By catalyst precarsor in an inert atmosphere by 500-1000 DEG C of high-temperature roasting so as to obtain N doping carbon-clad metal
The hydrogenation catalyst of nickel.
2. the preparation method of hydrogenation catalyst according to claim 1, it is characterised in that step（1）Described in nickel salts
For nickel nitrate, nickel chloride or nickel acetate；The load capacity of nickel is 1-14 %.
3. the preparation method of hydrogenation catalyst according to claim 1, it is characterised in that step（1）The load capacity of middle nickel is
4-8 %。
4. the preparation method of hydrogenation catalyst according to claim 1, it is characterised in that step（2）Described in nitrogenous chemical combination
Thing is urea, melamine, dicyandiamide, pyrroles, polypyrrole, the one or more in Lauxite and polyvinylpyrrolidone；
The mass ratio of ethylenediamine and carbon tetrachloride is 1:1-1:10；The mass ratio of glucose and nitrogen-containing compound is 1:4-1:20.
5. the preparation method of hydrogenation catalyst according to claim 1, it is characterised in that step（2）Described in ethylenediamine with
The mass ratio of carbon tetrachloride is 1:2-1:4；The mass ratio of glucose and nitrogen-containing compound is 1:4-1:8.
6. claim 1 gained hydrogenation catalyst is used for the purposes for being catalyzed hydrogenation of chloronitrobenzene synthesis para-aminophenol reaction.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109264706A (en) * | 2018-10-16 | 2019-01-25 | 李红莉 | A kind of method of the three-D nano-porous graphene powder of chemical vapour deposition technique controllable preparation |
| CN109305881A (en) * | 2017-07-28 | 2019-02-05 | 中国石油化工股份有限公司 | A kind of synthetic method of alcohol compound |
| CN112191265A (en) * | 2020-10-29 | 2021-01-08 | 武汉工程大学 | Nitrogen-doped carbon-supported copper/cerium dioxide composite catalyst and preparation method and application thereof |
| WO2021078112A1 (en) * | 2019-10-21 | 2021-04-29 | 中国石油化工股份有限公司 | Carbon-coated nickel oxide nanocomposite material, preparation method therefor and use thereof |
| CN114130395A (en) * | 2021-11-25 | 2022-03-04 | 西北民族大学 | Preparation method of magnetic super-hydrophobic nickel-carbon nano composite catalytic material based on catalytic synthesis of amine compounds |
| CN114308024A (en) * | 2021-12-31 | 2022-04-12 | 浙江工业大学 | Preparation method and application of carbon-doped coated platinum catalyst |
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Cited By (12)
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| CN109305881A (en) * | 2017-07-28 | 2019-02-05 | 中国石油化工股份有限公司 | A kind of synthetic method of alcohol compound |
| CN109305880A (en) * | 2017-07-28 | 2019-02-05 | 中国石油化工股份有限公司 | A kind of synthetic method of alcohol compound |
| CN109305890A (en) * | 2017-07-28 | 2019-02-05 | 中国石油化工股份有限公司 | A kind of synthetic method of alcohol compound |
| CN109305881B (en) * | 2017-07-28 | 2021-09-07 | 中国石油化工股份有限公司 | Synthetic method of alcohol compound |
| CN109305880B (en) * | 2017-07-28 | 2021-09-07 | 中国石油化工股份有限公司 | Synthetic method of alcohol compound |
| CN109305890B (en) * | 2017-07-28 | 2021-09-07 | 中国石油化工股份有限公司 | Synthetic method of alcohol compound |
| CN109264706A (en) * | 2018-10-16 | 2019-01-25 | 李红莉 | A kind of method of the three-D nano-porous graphene powder of chemical vapour deposition technique controllable preparation |
| WO2021078112A1 (en) * | 2019-10-21 | 2021-04-29 | 中国石油化工股份有限公司 | Carbon-coated nickel oxide nanocomposite material, preparation method therefor and use thereof |
| CN112191265A (en) * | 2020-10-29 | 2021-01-08 | 武汉工程大学 | Nitrogen-doped carbon-supported copper/cerium dioxide composite catalyst and preparation method and application thereof |
| CN114130395A (en) * | 2021-11-25 | 2022-03-04 | 西北民族大学 | Preparation method of magnetic super-hydrophobic nickel-carbon nano composite catalytic material based on catalytic synthesis of amine compounds |
| CN114308024A (en) * | 2021-12-31 | 2022-04-12 | 浙江工业大学 | Preparation method and application of carbon-doped coated platinum catalyst |
| CN114308024B (en) * | 2021-12-31 | 2023-09-05 | 浙江工业大学 | Preparation method and application of carbon-doped coated platinum catalyst |
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