CN1096294C - Catalyst for preparing metaphenylene dimethylamine - Google Patents
Catalyst for preparing metaphenylene dimethylamine Download PDFInfo
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- CN1096294C CN1096294C CN00111717A CN00111717A CN1096294C CN 1096294 C CN1096294 C CN 1096294C CN 00111717 A CN00111717 A CN 00111717A CN 00111717 A CN00111717 A CN 00111717A CN 1096294 C CN1096294 C CN 1096294C
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Abstract
The present invention relates to a catalyst for preparing metaphenylene dimethylamine, which mainly solves the defects of short catalyst life and high reaction pressure in the existing literatures. The present invention adopts modified Raney nickel as the catalyst, and tungsten, rare earth metals and at least one element out of Cr, Mo, Sn, Fe, Cu, Zr and Ti are introduced onto the Raney nickel, so that the problems are well solved. Therefore, the present invention can be used in industrial production.
Description
The present invention relates to a kind of catalyst for preparing m-xylene diamine.
M-xylene diamine (English name m-xylylenediamine or α, α-diamine-m-xylene, molecular formula C
8H
12N
2, 14 ℃ of fusing points, 248 ℃ of boiling points) and be a kind of colourless, have the liquid of almond flavor.M-xylene diamine is the epoxy curing agent of excellent performance, large usage quantity, it is again a kind of important Organic Ingredients intermediate, be mainly used in and make dimethylbenzene nylon resin (MXD6), photo-plastics, rubber chemicals, function epoxy resin polyurethane resin and coating etc.In addition, also can be used for aspects such as agricultural chemicals, fibre finish agent, antirust agent, chelating agent, lubricant, paper conversion agent.From the synthetic m-xylene diamine of isophthalodinitrile catalytic hydrogenation, existing lot of documents report.Because reasons such as pressure height (greater than 20.0MPa), feed stock conversion are low, reaction selectivity difference and catalyst life are short still exist many problems so far.Introduced a kind of method of reducing of aromatic nitriles among the clear 56-63944 of document.When being raw material with the isophthalodinitrile in the document, under the carbon dioxide coexistence, with 5% (weight) palladium/Al
2O
3Being catalyst, is under 60～78 ℃ of conditions in reaction temperature, hydrogenating reduction 60 minutes, and the yield that obtains the product m-xylene diamine is 86.6%, its catalyst/isophthalodinitrile (weight ratio) is 10%.Introduced a kind of technology of producing catalyst in the document US 4343722.It is to be catalyst with the cobalt octacarbonyl, and its catalyst/isophthalodinitrile (weight ratio) is 7.6～12.5%, and reaction temperature is about 160 ℃, and reaction pressure is up to 26.0MPa.It is solvent with the meta-xylene, and liquefied ammonia is inhibitor, m-xylene diamine yield about 94～96%.Do not relate to the life of catalyst problem in addition in the document.Introduced a kind of preparation method of dimethylphenylene diamine in the document US 4482741.Titanium with the cobalt and 4% (weight) of 60% (weight) in the document is carried on the solid carrier as catalyst.With the m-xylene diamine is solvent, reaction is 8 hours under reaction pressure 7.5MPa condition, wherein catalyst/isophthalodinitrile weight ratio is 11.7%, use for the first time, the yield of its m-xylene diamine is 88%, when circulation was used for the second time, the yield of its m-xylene diamine was 94%, had only reported the situation of catalyst circulation use secondary in addition in the document.Introduced a kind of manufacture method of primary amine among the document JP 54-41804.Use skeleton nickel to make major catalyst in the document, the co-catalyst composition is selected from metals such as Fe, Cr, Pb, Mn.In the embodiment, use above-mentioned catalyst, in 70 ℃ of temperature, pressure is to react under 11.0 ± 0.5MPa condition, and its isophthalodinitrile conversion ratio reaches 98.8%, the m-xylene diamine yield is 95.5%, but in the document, exist reaction pressure higher, catalyst life is shorter, when using for the second time, its active significantly reduced shortcoming.
The objective of the invention is in order to overcome in the conventional art, reaction pressure is higher, and the shortcoming that catalyst life is short provides a kind of catalyst of new preparation m-xylene diamine.It is low that this catalyst has suitable reaction pressure, the catalyst long service life, and keep the characteristics of high m-xylene diamine yield.
The objective of the invention is to realize: a kind of catalyst for preparing m-xylene diamine by following technical scheme, comprise skeleton nickel, tungsten and be selected from the co-catalyst of at least a and rare earth metal among Cr, Mo, Sn, Fe, Cu, Zr and the Ti, wherein with atomic ratio measuring with respect to Ni, the consumption of tungsten is 0.001～1.0%, being selected from consumption at least a among Cr, Mo, Sn, Fe, Cu, Zr and the Ti is 0～3%, and the consumption of rare earth metal is 0～0.2%.
With respect to the atomic ratio measuring of Ni, the preferable range of tungsten consumption is 0.001～0.5% in the technique scheme, and the more preferably scope of tungsten consumption is 0.001～0.1%; The preferable range of rare earth metal consumption is for being selected from 0.0001～0.05%.Rare earth metal is preferably from Ce, La, Pr or Sm, and more preferably scheme is La.
Method for preparing catalyst of the present invention is as follows:
At first nickel-aluminium alloy is reacted with the sodium hydroxide solution of required reacting dose earlier, water cleans to neutral, add the tungsten of aequum then and be selected from that at least a and rare earth metal carries out modification among Cr, Mo, Sn, Fe, Cu, Zr and the Ti, through washing, ethanol washing 2～3 times and be kept in the ethanol.
Because aromatic nitriles catalytic hydrogenation system aromatic amine, reaction experience hydrogenation generates the pilot process of imines.The reactivity of imines is very high, easily take place further to react with reaction intermediate and principal product, by condensation, ammonia is separated, the crosslinked reaction generation secondary amine that waits, by-product such as tertiary amine and high-boiling components, influence reaction conversion ratio, selectivity and yield, therefore must improve the reactivity of catalyst, strengthen catalyst to the absorption of unsaturated intermediates such as imines or suppress its desorption, reduce the amount of free imines in the course of reaction as far as possible, improve hydrogenation reaction speed, shorten the reaction time, reduce the possibility that side reaction takes place, thereby reach the purpose of isophthalodinitrile high conversion and primary amine high selectivity.From isophthalodinitrile hydrogenation reaction course, the interaction of intermediate product imines that desorption gets off on the catalyst and false add hydrogen product can aggravate the formation of high-boiling components.High-boiling components is adsorbed on catalyst surface can further reduce absorption to imines etc., forms vicious circle, causes the very fast inactivation of catalyst, therefore must strengthen the adsorption strength of catalyst active center.On the other hand, because the skeletal nickel catalyst activated centre is too much, the hydrogen supply amount is big, can cause the aggravation of product hydrogenolysis.The present invention is by introducing tungsten in skeleton nickel, strengthened the stability of catalyst, introduce at least a Cr of being selected from, Mo, Sn, Fe, Cu, Zr and Ti composition and rare earth metal simultaneously, catalyst and its main reaction are adapted, strengthened the absorption of catalyst to unsaturated compounds such as imines, reduce the activity and the number of absorption hydrogen simultaneously, suppressed side reaction, thereby improved catalyst to the active of main reaction and improved reaction conversion ratio and yield.Use catalyst of the present invention, be used for the reaction of isophthalodinitrile hydrogenation preparing m-xylene diamine, at 70 ℃ of reaction temperatures, reaction pressure 6.0MPa, when being solvent with methyl alcohol-toluene, reacted 90～120 minutes, its isophthalodinitrile conversion ratio reaches as high as 99.82%, and the m-xylene diamine yield can reach 96.7%, and the catalyst one way can reach 3～4 times service life, than 1～2 time of bibliographical information in the past, increased closely 200%, obtained effect preferably.
The present invention is further elaborated below by embodiment.[embodiment 1]
In 300 milliliters of reactors, with the modified raney ni is catalyst, comprise tungsten in the catalyst, wherein with atomic ratio measuring with respect to Ni, Ni: W is 100: 1, isophthalodinitrile and hydrogen are 70 ℃ of reaction temperatures, and reaction pressure is 6.0MPa, and one methyl alcohol-toluene is solvent, methyl alcohol wherein: toluene (volume/volume)=1: 2.5, solvent: isophthalodinitrile (w/w) is 4: 1, and catalyst/isophthalodinitrile is 11.0% (weight), and other adds 0.2 gram NaOH is reaction promoter, low whipping speed is under 500 rev/mins, reacted 120 minutes, the isophthalodinitrile conversion ratio is 98.6%, and the m-xylene diamine yield is 94.7% (weight).After this catalyst repeated use 4 times, its isophthalodinitrile conversion ratio is 98.4%, and the m-xylene diamine yield is 94.4%, does not fall as follows.[embodiment 2～6]
According to each operating condition and the step of embodiment 1, just change the composition of catalyst, its reaction result is listed in table 1.[comparative example 1]
According to each operating condition and the step of embodiment 1, just change the composition of catalyst, its reaction result is listed in table 1.
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Claims (6)
1, a kind of catalyst for preparing m-xylene diamine, comprise skeleton nickel, tungsten and be selected from least a and co-catalyst that is selected from the rare earth metal of Ce, La, Pr or Sm among Cr, Mo, Sn, Fe, Cu, Zr and the Ti, wherein with atomic ratio measuring with respect to Ni, the consumption of tungsten is 0.001～1.0%, being selected from consumption at least a among Cr, Mo, Sn, Fe, Cu, Zr and the Ti is 0～3%, and the consumption of rare earth metal is 0～0.2%.
2,, it is characterized in that with atomic ratio measuring the consumption of tungsten is 0.001～0.5% with respect to Ni according to the catalyst of the described preparation m-xylene diamine of claim 1.
3,, it is characterized in that with atomic ratio measuring the consumption of tungsten is 0.001～0.1% with respect to Ni according to the catalyst of the described preparation m-xylene diamine of claim 2.
4,, it is characterized in that with atomic ratio measuring the consumption of rare earth metal is 0.0001～0.05% with respect to Ni according to the catalyst of the described preparation m-xylene diamine of claim 1.
5,, it is characterized in that rare earth metal is selected from La according to the catalyst of the described preparation m-xylene diamine of claim 1.
6,, it is characterized in that with atomic ratio measuring being selected from consumption at least a among Cr, Mo, Sn, Fe, Cu, Zr and the Ti is 0.5～2% with respect to Ni according to the catalyst of the described preparation m-xylene diamine of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00111717A CN1096294C (en) | 2000-02-24 | 2000-02-24 | Catalyst for preparing metaphenylene dimethylamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00111717A CN1096294C (en) | 2000-02-24 | 2000-02-24 | Catalyst for preparing metaphenylene dimethylamine |
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| CN1310043A CN1310043A (en) | 2001-08-29 |
| CN1096294C true CN1096294C (en) | 2002-12-18 |
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| CN00111717A Expired - Fee Related CN1096294C (en) | 2000-02-24 | 2000-02-24 | Catalyst for preparing metaphenylene dimethylamine |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101955432B (en) * | 2010-04-20 | 2013-02-13 | 南通泰禾化工有限公司 | Method for preparing m-xylylenediamine by intermittent hydrogenation in stirred tank |
| CN114749187A (en) * | 2022-04-24 | 2022-07-15 | 河南尤尼特化工新材料有限公司 | Metal framework catalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49133339A (en) * | 1973-05-02 | 1974-12-21 | ||
| US4343722A (en) * | 1980-04-03 | 1982-08-10 | Mitsubishi Gas Chemical Company, Inc. | Process for producing catalyst |
| US4482741A (en) * | 1984-01-09 | 1984-11-13 | Uop Inc. | Preparation of xylylenediamine |
-
2000
- 2000-02-24 CN CN00111717A patent/CN1096294C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49133339A (en) * | 1973-05-02 | 1974-12-21 | ||
| US4343722A (en) * | 1980-04-03 | 1982-08-10 | Mitsubishi Gas Chemical Company, Inc. | Process for producing catalyst |
| US4482741A (en) * | 1984-01-09 | 1984-11-13 | Uop Inc. | Preparation of xylylenediamine |
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| CN1310043A (en) | 2001-08-29 |
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