CN103638940A - Catalyst for synthesizing m-phenylenediamine from m-dinitrobenzene by hydrogenation reaction and application thereof - Google Patents
Catalyst for synthesizing m-phenylenediamine from m-dinitrobenzene by hydrogenation reaction and application thereof Download PDFInfo
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- CN103638940A CN103638940A CN201310548291.3A CN201310548291A CN103638940A CN 103638940 A CN103638940 A CN 103638940A CN 201310548291 A CN201310548291 A CN 201310548291A CN 103638940 A CN103638940 A CN 103638940A
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Abstract
The invention provides a catalyst for synthesizing m-phenylenediamine from m-dinitrobenzene by hydrogenation reaction, wherein the catalyst comprises a core structure and a shell structure, the core structure is a MnO2-NiO-ZrO2 composite metal oxide, and the shell structure is MnO2-NiO-ZrO2-SiO2-TiO2. The catalyst with a core-shell structure has advantages of simple preparation technology and low cost, a special structure and mutual effects of Mn, Ni and Zr greatly raise the activity of the catalyst, and the conversion rate of m-dinitrobenzene and the yield of the m-phenylenediamine are all higher than 97%.
Description
Technical field
The present invention relates to catalyst and the application thereof of the synthetic m-phenylene diamine (MPD) reaction of a kind of MDNB hydrogenation, belong to catalysis technical field.
Background technology
M-phenylene diamine (MPD) is a kind of important Organic Chemicals, is widely used as the intermediate of azo dyes, fur dyes, reactive dye and sulfur dye in dye industry; In addition, also for mordant, hair dye, aobvious
Synthesizing of toner, rubber chemicals, epoxy curing agent, petroleum additive, accelerator for cement slurry and dissolving metal agent etc.Industrial production m-phenylene diamine (MPD) is to adopt MDNB iron powder reducing method substantially.The method is with a long history, and technique is simple, technology maturation, but production cost is higher, and yield is lower, and produces a large amount of reluctant iron mud and waste water that contains arylamine, and environmental pollution is serious.By comparison, catalytic hydrogenation rule has product yield high, and quality is good, and cost is low, and the three wastes are few, are conducive to the advantages such as protection of the environment, therefore be widely adopted at present.
The conventional catalyst of catalytic hydrogenation method has Raney Ni and noble metal, and the former can cause environmental pollution in the preparation, and the latter is expensive.Therefore, development cost is low, activity is high and eco-friendly MDNB catalytic hydrogenation catalyst has important social benefit and using value.The catalyst of nucleocapsid structure is a class catalyst that starts in recent years research and development, it has unique structure, owing to showing very high conversion ratio and selective in reaction, and improved to a great extent service life of catalyst and stability and extensively concerned, and its application in MDNB hydrogenation there is not yet report so far.
Summary of the invention
The present invention overcomes the ubiquitous problem of catalyst of the prior art; provide that a kind of preparation cost is low, conversion ratio is high; the catalyst of the synthetic m-phenylene diamine (MPD) reaction of MDNB hydrogenation of long service life, the present invention also protects the application of this catalyst in the synthetic m-phenylene diamine (MPD) reaction of MDNB hydrogenation.
In order to address the above problem, the technical solution used in the present invention is as follows:
The catalyst of the synthetic m-phenylene diamine (MPD) reaction of a kind of MDNB hydrogenation, this catalyst has nuclear structure and shell structure, wherein nuclear structure is MnO2-NiO-ZrO2 composite metal oxide, and shell structure is MnO2-NiO-ZrO2-SiO2-TiO2, prepares by the following method:
(1) prepare nuclear structure: adopt coprecipitation to prepare MnO2-NiO-ZrO2 composite metal oxide, after by the soluble-salt solution of manganese, nickel and zirconium, under stirring, also stream mixes, precipitates with aqueous slkali, through overaging, and be washed with distilled water to neutrality, the composite metal oxide obtaining is dried at 80-120 ℃, roasting 6-10h at 350-500 ℃, then by its moulding, make 10-30 object particle standby;
(2) prepare shell structure: the mixed liquor of soluble-salt solution, ethyl orthosilicate and the butyl titanate of manganese, nickel and zirconium is stirred, the MnO2-NiO-ZrO2 composite metal oxide particle that step (1) is prepared adds in above-mentioned mixed liquor, High Rotation Speed stirs and makes it dispersed, proceed to again stainless steel cauldron and react 5-12h at 150-200 ℃, the product obtaining obtains target catalyst after filtering, repeatedly wash, being dried, and its outer shell thickness is 2-10 μ m.
Preferably, in the soluble-salt solution of step (1), the mol ratio of Mn, Ni, Zr is 1: (1-2): 1.
Preferably, aqueous slkali is NaOH or potassium hydroxide.
Preferably, in step (2), Si/Ti mol ratio is 3: 1-1: 1.
Preferably, in step (2), the mol ratio of Mn, Ni, Zr, Si and Ti is 1: (1-2): 1: 1: 1.
Preferably, the soluble-salt solution of manganese, nickel and zirconium is selected from nitrate.
The present invention also protects the catalyst of this nucleocapsid structure to synthesize the application in m-phenylene diamine (MPD) reaction at MDNB hydrogenation; wherein reaction pressure is 2-5MP, and reaction temperature is 80-120 ℃, and ratio of solvent is 1-5: 1; hydrogen flow rate is 40-70ml/h, and flow rate of liquid is 1-50ml/h.
Compared with prior art, the present invention has following significant advantage:
Catalyst of the present invention be take MnO2-NiO-ZrO2 composite metal oxide as nuclear structure, take MnO2-NiO-ZrO2-SiO2-TiO2 as shell structure, and preparation technology is simple, and cost is low; Because the introducing of silicon and titanium makes the concentration ratio kernel of outer active component low, like this, in course of reaction, because the active component concentration of catalyst outer surface is low, corresponding activity is also low, effectively suppress emerging of focus and gathering of energy, reduced the production rate of accessory substance, effectively improved the selective of target product; And after reaction after a while, although the active component of catalyst surface is lost, the active component of internal layer is still higher, make catalyst can keep higher activity, the life-span is effectively extended; This catalyst utilizes the interaction between Mn, Ni, Zr in addition, realizes best proportioning, the activity of catalyst activity has been had and increase substantially, and the conversion ratio of MDNB and the yield of m-phenylene diamine (MPD) are all higher than 97%.
The specific embodiment
With specific embodiment, the application of this O composite metallic oxide catalyst in methanol dehydration dimethyl ether-preparing reaction is described below, but scope of the present invention is not limited to these embodiment.
Embodiment 1: the preparation of catalyst 1
(1) kernel of Kaolinite Preparation of Catalyst first, to contain platinous chloride, silver nitrate and zinc chloride adds in 1000ml pure water according to mol ratio, fully be uniformly mixed, form active component slurries A, wherein the mol ratio of the element of the first component and second component is 1: 3;
(2) active component slurries A is carried out form after co-precipitation the kernel slurry of catalyst, at 70 ℃, dry, moulding, at 300 ℃, roasting 8h roasting obtains the kernel of catalyst;
(3) follow the skin of Kaolinite Preparation of Catalyst, to contain plumbi nitras, silver nitrate, zinc chloride and lanthanum chloride adds in 1000ml pure water according to mol ratio again, fully be uniformly mixed, form active component slurries B, wherein the element mol ratio of the first component, second component and the 3rd component is 1: 3: 3;
(4) last, the active component slurries B of preparation is coated on the kernel of catalyst, at 90 ℃, to dry, moulding obtains finished catalyst 1 after roasting 10h at 450 ℃.
The kernel diameter of the catalyst 1 obtaining is 1mm, and outer field bed thickness is 0.5mm.
Embodiment 2: the preparation of catalyst 2
(1) kernel of Kaolinite Preparation of Catalyst first, to contain platinum nitrate, palladium sulfate and copper chloride adds in 1000ml pure water according to mol ratio, fully be uniformly mixed, form active component slurries A, wherein the mol ratio of the element of the first component and second component is 1: 5;
(2) active component slurries A is carried out form after co-precipitation the kernel slurry of catalyst, at 70 ℃, dry, moulding, at 300 ℃, roasting 8h roasting obtains the kernel of catalyst;
(3) follow the skin of Kaolinite Preparation of Catalyst, to contain platinum nitrate, palladium sulfate, copper chloride and lanthanum chloride adds in 1000ml pure water according to mol ratio again, fully be uniformly mixed, form active component slurries B, wherein the element mol ratio of the first component, second component and the 3rd component is 1: 5: 3;
(4) last, the active component slurries B of preparation is coated on the kernel of catalyst, at 90 ℃, to dry, moulding obtains finished catalyst 2 after roasting 10h at 450 ℃.
The kernel diameter of the catalyst 1 obtaining is 1mm, and outer field bed thickness is 0.5mm.
Comparative example 1:
Take the inner nuclear material of catalyst 1 as being comparative catalyst 1, make the ball that diameter is 1mm.
Comparative example 2:
The skin of catalyst 1 of take is comparative catalyst 2, makes the ball that diameter is 1mm.
Comparative example 3:
With HZSM-5 catalyst 3 as a comparison.
Embodiment 3: the performance measurement by above-mentioned catalyst for methanol dehydration dimethyl ether-preparing reaction.Adopt fixed bed reactors, reaction temperature is 200 ℃, and pressure is 1Mpa, and weight (hourly) space velocity (WHSV) is 5h-1, take trade effluent ethanol as reaction raw materials, investigates the performance of above-mentioned catalyst in preparing dimethyl ether from methanol reaction, the results are shown in following table 1 and table 2.
The reactivity worth of table 1 catalyst
| Application examples | Methanol conversion (%) | Dimethyl ether selective (%) |
| Embodiment 1 | 95.4 | 100 |
| Embodiment 2 | 94.2 | 100 |
| Comparative example 1 | 84.0 | 98.5 |
| Comparative example 2 | 81.2 | 98.0 |
| Comparative example 3 | 77.1 | 95.1 |
The stability of table 2 catalyst 1
| Running time | Reaction temperature | Reaction pressure | Weight (hourly) space velocity (WHSV) | Methanol conversion |
| (h) | (℃) | (Mpa) | (h -1) | (％) |
| 1 | 200 | 1 | 5 | 95.4 |
| 100 | 200 | 1 | 5 | 95.4 |
| 200 | 200 | 1 | 5 | 95.2 |
| 400 | 200 | 1 | 5 | 94.0 |
By the above results, can be seen, compared with prior art, reactivity worth and the stability of the catalyst that the present invention prepares are all greatly improved, and successive reaction is after 400 hours, and the activity of catalyst is still very high, not significant decline.
Claims (6)
1. a MDNB hydrogenation synthesizes the catalyst of m-phenylene diamine (MPD) reaction, this catalyst has nuclear structure and shell structure, wherein nuclear structure is MnO2-NiO-ZrO2 composite metal oxide, and shell structure is MnO2-NiO-ZrO2-SiO2-TiO2, prepares by the following method:
(1) prepare nuclear structure: adopt coprecipitation to prepare MnO2-NiO-ZrO2 composite metal oxide, after by the soluble-salt solution of manganese, nickel and zirconium, under stirring, also stream mixes, precipitates with aqueous slkali, through overaging, and be washed with distilled water to neutrality, the composite metal oxide obtaining is dried at 80-120 ℃, roasting 6-10h at 350-500 ℃, then by its moulding, make 10-30 object particle standby.
(2) prepare shell structure: the mixed liquor of soluble-salt solution, ethyl orthosilicate and the butyl titanate of manganese, nickel and zirconium is stirred, the MnO2-NiO-ZrO2 composite metal oxide particle that step (1) is prepared adds in above-mentioned mixed liquor, High Rotation Speed stirs and makes it dispersed, proceed to again stainless steel cauldron and react 5-12h at 150-200 ℃, the product obtaining obtains target catalyst after filtering, repeatedly wash, being dried, and its outer shell thickness is 2-10 μ m.
2. catalyst according to claim 1, is characterized in that the mol ratio of Mn, Ni, Zr in the soluble-salt solution of step (1) is 1: (1-2): 1.
3. according to the catalyst described in claim 1-2, it is characterized in that in step (2), Si/Ti mol ratio is 3: 1-1: 1.
4. according to the catalyst described in claim 1-3, it is characterized in that the mol ratio of Mn, Ni, Zr, Si and Ti in step (2) is 1: (1-2): 1: 1: 1.
5. according to the catalyst described in claim 1-4, it is characterized in that the soluble-salt solution of manganese, nickel and zirconium is selected from nitrate.
6. the application in the synthetic m-phenylene diamine (MPD) reaction of MDNB hydrogenation according to the catalyst described in claim 1-5, it is characterized in that reaction pressure is 2-5MP, reaction temperature is 80-120 ℃, and ratio of solvent is 1-5: 1, hydrogen flow rate is 40-70ml/h, and flow rate of liquid is 1-50ml/h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108855126A (en) * | 2017-05-11 | 2018-11-23 | 中国石油化工股份有限公司 | A kind of shell core formula catalyst and preparation method synthesizing m-phenylene diamine (MPD) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1439456A (en) * | 2003-04-08 | 2003-09-03 | 天津大学 | Catalyst for producing melaphenylene from m-dinitrobenze by liquid phase hydrogenation and preparation thereof |
| CN101227973A (en) * | 2005-06-16 | 2008-07-23 | 约翰森·马瑟公开有限公司 | Catalyst and process for its manufacture |
| CN101279870A (en) * | 2008-05-10 | 2008-10-08 | 大连理工大学 | Application of multicomponent amorphous alloy to preparing arylamine by catalytic hydrogenation of aromatic nitro compound |
| CN101972648A (en) * | 2010-09-10 | 2011-02-16 | 常州大学 | Modified Mn-Zr catalyst as well as preparation method and application thereof to preparing dimethyl ether |
| CN102989469A (en) * | 2011-09-08 | 2013-03-27 | 中国石油天然气股份有限公司 | Multi-metal oxide catalyst and preparation method thereof |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1439456A (en) * | 2003-04-08 | 2003-09-03 | 天津大学 | Catalyst for producing melaphenylene from m-dinitrobenze by liquid phase hydrogenation and preparation thereof |
| CN101227973A (en) * | 2005-06-16 | 2008-07-23 | 约翰森·马瑟公开有限公司 | Catalyst and process for its manufacture |
| CN101279870A (en) * | 2008-05-10 | 2008-10-08 | 大连理工大学 | Application of multicomponent amorphous alloy to preparing arylamine by catalytic hydrogenation of aromatic nitro compound |
| CN101972648A (en) * | 2010-09-10 | 2011-02-16 | 常州大学 | Modified Mn-Zr catalyst as well as preparation method and application thereof to preparing dimethyl ether |
| CN102989469A (en) * | 2011-09-08 | 2013-03-27 | 中国石油天然气股份有限公司 | Multi-metal oxide catalyst and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108855126A (en) * | 2017-05-11 | 2018-11-23 | 中国石油化工股份有限公司 | A kind of shell core formula catalyst and preparation method synthesizing m-phenylene diamine (MPD) |
| CN108855126B (en) * | 2017-05-11 | 2021-06-01 | 中国石油化工股份有限公司 | Shell-core catalyst for synthesizing m-phenylenediamine and preparation method thereof |
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