CN109772343A - A kind of preparation method of low cost selective hydrogenation Cracking catalyst - Google Patents
A kind of preparation method of low cost selective hydrogenation Cracking catalyst Download PDFInfo
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- CN109772343A CN109772343A CN201711117552.0A CN201711117552A CN109772343A CN 109772343 A CN109772343 A CN 109772343A CN 201711117552 A CN201711117552 A CN 201711117552A CN 109772343 A CN109772343 A CN 109772343A
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Abstract
The present invention provides a kind of preparation methods of inexpensive selective hydrogenation Cracking catalyst, and preparation method is: (1) using terbium oxide as carrier to load metal nickel salt, then roasting obtains the nickel oxide of terbium oxide load in air atmosphere；(2) then the compound that step (1) obtains uniformly is mixed with diacetyl ammonia and carbon tetrachloride, back flow reaction obtains the catalyst precarsor of cladding polymer with nitrogen in dimethylbenzene；Or the compound and glucose and nitrogenous compound that step (1) obtains are mixed to get catalyst precarsor；(3) catalyst precarsor is passed through to 500-1000 DEG C of high-temperature roasting in an inert atmosphere to obtain the hydrogenation catalyst of nitrogen-doped carbon cladding metallic nickel.The catalyst is used to be catalyzed the purposes of hydrogenation of chloronitrobenzene synthesis para-aminophenol, and nitrobenzene conversion rate and para-aminophenol selectively can reach 100%.
Description
Technical field
The present invention relates to a kind of preparation methods of inexpensive selective hydrogenation Cracking catalyst.
Background technique
Para-aminophenol is a kind of important organic intermediate, is widely used in the fields such as medicine, dyestuff and rubber.Mesh
Before, the industrial process for producing para-aminophenol is made mainly in strongly acidic solution by catalysis one step of hydrogenation of chloronitrobenzene
, catalyst used in this process conditions is usually the noble metal platinum or palladium catalyst loaded, and the conversion ratio of nitrobenzene can
Up to 90%, while the selectivity of para-aminophenol is about 85%.However (the usually 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 be also lost, to make to catalyst
Adverse effect is brought in terms of control with service life and production cost.
In order to improve the production technology under this strong acidic condition, people are it is also proposed that with solid acid substitution fluid sulphuric acid in water
Catalysis hydrogenation of chloronitrobenzene synthesis para-aminophenol is carried out in solution, so that the loss of active component is reduced, however this technique is set
Meter needs to be added a large amount of solid acid, and noble metal active component is still an exposure in acidic 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, exploring a kind of new structural catalyst based on base metal seems significant.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of inexpensive selective hydrogenation Cracking catalyst, hydrogen should be added to urge
Agent is obtained based on base metal, and catalysis hydrogenation of chloronitrobenzene synthesizes para-aminophenol, has high selectivity.In order to realize above-mentioned hair
Improving eyesight, the invention adopts the following technical scheme:
A kind of preparation method of low cost selective hydrogenation Cracking catalyst, steps are as follows:
(1) using terbium oxide as carrier to load metal nickel salt, then roasting obtains the oxygen of terbium oxide load in air atmosphere
Change nickel；Calcining time is 4 hours in air atmosphere；
(2) then the compound that step (1) obtains uniformly is mixed with diacetyl ammonia and carbon tetrachloride, is returned in dimethylbenzene
Stream reaction obtains the catalyst precarsor of cladding polymer with nitrogen；Or the compound for obtaining step (1) and glucose and nitrogenous
Compound is mixed to get catalyst precarsor；
(3) catalyst precarsor is passed through to 500-1000 DEG C of high-temperature roasting in an inert atmosphere to obtain nitrogen-doped carbon cladding
The hydrogenation catalyst of metallic nickel, preferred 600-800 DEG C of maturing temperature in the step.
The nickel salts are nickel nitrate, nickel chloride or nickel acetate；
With terbium oxide carried metal nickel salt in step (1), the load capacity of nickel is 1-14%, preferably 4-8%；
The nitrogenous compound is urea, melamine, dicyandiamide, pyrroles, polypyrrole, Lauxite and polyvinyl pyrrole
One of alkanone is a variety of.
In step (2), relative to the nickel oxide of every gram of terbium oxide load, the mass ratio of diacetyl ammonia and carbon tetrachloride is 1:
1-1: 10, preferably 1: 2-1: 4；
In step (2), relative to the nickel oxide of every gram of terbium oxide load, the mass ratio of glucose and nitrogenous compound is 1:
4-1: 20, preferably 1: 4-1: 8.
Above-mentioned catalyst is used to be catalyzed the purposes of hydrogenation of chloronitrobenzene synthesis 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 is used for catalysis hydrogenation of chloronitrobenzene synthesis to ammonia
Base phenol shows excellent catalytic performance.The process cost is cheap, simple process, for exploitation catalysis hydrogenation of chloronitrobenzene synthesis
The high performance catalyst of para-aminophenol provides new thinking.
Specific embodiment
Technical solution of the present invention is illustrated below with reference to embodiment:
The acquisition of carrier terbium oxide employed in the present embodiment can be obtained without particular/special requirement using conventional method.
Specifically, the carrier terbium oxide obtains in the following manner weighs 16.88g sodium hydroxide and is dissolved in 30mL water, so
After weigh 1.96g terbium nitrate be added 40mL water in stirring dissolve terbium nitrate, configured sodium hydroxide solution is slowly added to
In terbium nitrate aqueous solution and continue to stir, 100 DEG C are cooled to room temperature after reaction 24 hours, and vacuum is dry after centrifuge washing is multiple
Dry carrier terbium oxide to obtain the final product.
Catalysis hydrogenation of chloronitrobenzene synthesis para-aminophenol carries 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 reaction kettle is filled with the hydrogen of 1.0Mpa after being repeated several times, stop heating after persistently stirring at 120 DEG C 2 hours, to
The hydrogen in reaction kettle is drained after being cooled to room temperature, and with being recovered by filtration to obtain catalyst after ammonium hydroxide 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) terbium oxide (CeO2) the broken sieving of carrier process, 20-40 mesh is chosen, incipient impregnation nickel nitrate aqueous solution obtains
The sample that load capacity to nickel is 6wt.%；After standing a period of time, 80 DEG C are dried under vacuum to after constant weight 450 in air atmosphere
Nickel oxide (the NiO/CeO for obtaining terbium oxide load for 4 hours is roasted at DEG C2)；
(2) 1g NiO/CeO is taken2Be added in round-bottomed flask, sequentially add 2.0g diacetyl ammonia and 4.0g carbon tetrachloride and
80mL dimethylbenzene, being warming up to 140 DEG C after being first warming up to 90 DEG C of reactions 4 hours again, the reaction was continued 4 hours, then stops heating to cold
But to sediment and drying is centrifugated out after room temperature, grinding obtains powdered product；
(3) then 600 DEG C of roastings obtain black grained catalyst (CN/Ni/CeO in 6 hours in nitrogen atmosphere2)。
It is used for catalysis hydrogenation of chloronitrobenzene synthesis para-aminophenol, wherein nitrobenzene conversion rate is 99%.P-aminophenyl
Phenol is selectively 100%.
Claims (4)
1. a kind of preparation method of low cost selective hydrogenation Cracking catalyst, which is characterized in that steps are as follows:
(1) using terbium oxide as carrier to load metal nickel salt, then roasting obtains the nickel oxide of terbium oxide load in air atmosphere；
(2) then the compound that step (1) obtains uniformly is mixed with diacetyl ammonia and carbon tetrachloride, is flowed back in dimethylbenzene anti-
It should obtain the catalyst precarsor of cladding polymer with nitrogen；Or the compound for obtaining step (1) and glucose and nitrogenous chemical combination
Object is mixed to get catalyst precarsor；
(3) catalyst precarsor is passed through to 500-1000 DEG C of high-temperature roasting in an inert atmosphere 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 nickel salts described in step (1)
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 the load capacity of nickel is in step (1)
4-8%.
4. the preparation method of hydrogenation catalyst according to claim 1, it is characterised in that nitrogenous chemical combination described in step (2)
Object is urea, melamine, dicyandiamide, pyrroles, polypyrrole, one of Lauxite and polyvinylpyrrolidone or a variety of；
The mass ratio of diacetyl ammonia and carbon tetrachloride is 1: 1-1: 10；The mass ratio of glucose and nitrogenous compound is 1: 4-1: 20.
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| CN201711117552.0A CN109772343A (en) | 2017-11-13 | 2017-11-13 | A kind of preparation method of low cost selective hydrogenation Cracking catalyst |
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| CN201711117552.0A CN109772343A (en) | 2017-11-13 | 2017-11-13 | A kind of preparation method of low cost selective hydrogenation Cracking catalyst |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114029055A (en) * | 2021-12-20 | 2022-02-11 | 中国科学院生态环境研究中心 | Catalyst, preparation method and application thereof |
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- 2017-11-13 CN CN201711117552.0A patent/CN109772343A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114029055A (en) * | 2021-12-20 | 2022-02-11 | 中国科学院生态环境研究中心 | Catalyst, preparation method and application thereof |
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| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190521 |
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| WD01 | Invention patent application deemed withdrawn after publication |